Resin composition, cured product, laminate, semiconductor device, and method for producing laminate

Abstract

The purpose of the present invention is to provide: a resin composition capable of obtaining a laminate having a high adhesive strength between two substrates when the two substrates are bonded and having high reliability; a cured product; a laminate comprising said cured product; a semiconductor device comprising said laminate; and a method for producing said laminate. The present invention pertains to a method for producing a laminate, the method comprising a step (I), a step (II), and a step (III) in this order, wherein: at least one among (B-1) a resin layer and (B-2) a resin layer is composed of a cured product of a resin composition (D); the resin composition (D) contains a resin (E) and a solvent; the resin (E) has a repeating unit represented by formula (1-A) or / and a repeating unit represented by formula (1-B); the resin (E) further has a repeating unit represented by formula (1-C) or / and a repeating unit represented by formula (1-D); and when the amount of all the repeating units contained in the resin (E) is 100 mol%, the total amount of the repeating unit represented by formula (1-A) and the repeating unit represented by formula (1-B) in the resin (E) is 80-99 mol%, and the total amount of the repeating unit represented by formula (1-C) and the repeating unit represented by formula (1-D) in the resin (E) is 1-10 mol%.

Description

Resin composition, cured product, laminate, semiconductor device, and method for producing laminate

[0001] The present invention relates to a resin composition, a cured product, a laminate, a semiconductor device, and a method for producing the laminate.

[0002] Conventionally, when electrically connecting semiconductor or MEMS (Micro Electro Mechanical Systems) chips to the outside world, protruding electrodes (bumps) made of gold or copper or the like have been formed and connected to a connection substrate or the like via solder. Techniques such as underfilling have been established to maintain insulation between electrodes. In recent years, as the number of electrodes connected to the outside world has increased significantly due to the high integration of chips, and electrode density has risen, attention has been drawn to hybrid bonding technology, which forms electrodes and insulating films on the same plane without forming bumps and connects them to the outside world by direct bonding (Patent Document 1). This technology enables high-density packaging with an electrode pitch of 10 μm or less.

[0003] Hybrid bonding is divided into two processes: the W2W (Wafer-to-Wafer) process, which bonds wafers together, and the C2W (Chip-to-Wafer) process, which bonds chips to wafers. In the C2W process, the insulating layer is made of a conventional SiO ２ A technique is known in which, instead of the above, a polyimide resin composition having a low elastic modulus is used to suppress voids caused by foreign matter that occur when chips are diced, thereby improving the reliability of the laminate (Patent Document 2).

[0004] JP-T-2006-517344 A JP-A-2023-136961 A

[0005] When polyimides with a higher average linear expansion coefficient than metal electrodes are used as insulating layers in hybrid bonding, the reliability of the laminate is reduced. Furthermore, polyimides with an average linear expansion coefficient similar to that of metal electrodes tend to have a high elastic modulus, which reduces the adhesive strength during hybrid bonding, making their application difficult.

[0006] In order to solve the above problems, the present invention has the following configuration.

[0007] [1] A method for producing a laminate, comprising steps (I), (II), and (III) in this order, wherein at least one of a (B-1) resin layer and a (B-2) resin layer is made of a cured product of a resin composition (D), and the resin composition (D) contains a resin (E) and a solvent, and the resin (E) has either or both of a repeating unit represented by formula (1-A) and a repeating unit represented by formula (1-B), and the resin (E) has either or both of a repeating unit represented by formula (1-C) and a repeating unit represented by formula (1-D), and when all repeating units contained in the resin (E) are taken as 100 mol %, the total of the repeating units represented by formula (1-A) and the repeating units represented by formula (1-B) in the resin (E) is 80 to 99 mol %, and the total of the repeating units represented by formula (1-C) and the repeating units represented by formula (1-D) in the resin (E) is 1 to 10 mol %. Step (I): Preparing a first substrate having an (A-1) metal electrode and an exposed (B-1) resin layer exposed on the same surface of the substrate body, and a second substrate having an (A-2) metal electrode and an exposed (B-2) resin layer or (C) inorganic insulating layer exposed on the same surface of the substrate body; Step (II): Activating the surfaces of the first substrate and the second substrate by plasma treatment or UV irradiation; Step (III): Bonding the first substrate and the second substrate by direct bonding, with at least a portion of the (A-1) metal electrode and the (A-2) metal electrode and at least a portion of the (B-1) resin layer facing the (B-2) resin layer or the (C) inorganic insulating layer.

[0008]

[0009] In formula (1-A), formula (1-B), formula (1-C) and formula (1-D), R １ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by formula (2). Each s independently represents an integer of 1 to 50. ８ and R ９ R each independently represents an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ４ ~R７ each independently represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. Each X independently represents a group represented by formula (3), and each Y independently represents a group represented by formula (4).

[0010]

[0011] In formula (2), R １０ is an alkyl group having 1 to 5 carbon atoms, R １１ represents an alkylidene group having 1 to 5 carbon atoms. * represents a bonding site. In formula (3), n is an integer of 0 to 3, and m is an integer of 1 to 2. * represents a bonding site. In formula (4), R ２ and R ３ each independently represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a carboxy group, a sulfonic acid group, or a mercapto group. p is an integer of 0 to 4, q is an integer of 0 to 4, and r is an integer of 0 to 2. Z is a bond, atom, or group selected from a single bond, an alkylene group having 1 to 12 carbon atoms, a halogenated alkylene group having 1 to 12 carbon atoms, a sulfonyl group, an S atom, an O atom, a CO group, and a COO group. * represents a bonding site.

[0012] [2] The method for producing a laminate according to [1], wherein the resin composition (D) contains 0.1 to 3 parts by mass of a compound represented by formula (5) relative to 100 parts by mass of the resin (E).

[0013]

[0014] In formula (5), R １２ , R １３ , R １４ and R １５ each independently represents a group having 1 to 5 carbon atoms, 0 to 2 oxygen atoms, and 0 to 1 nitrogen atom, or a hydrogen atom.

[0015] [3] The method for producing a laminate according to [1] or [2], wherein the step (II) is a step of activating the surfaces of the first substrate and the second substrate by plasma treatment in a temperature range of 30 to 100°C.

[0016] [4] A method for producing a laminate, comprising steps (I), (II), and (III) in this order, wherein at least one of the (B-1) resin layer and the (B-2) resin layer has an average linear expansion coefficient of 0 to 40 ppm / K in a temperature range of 50 to 150°C, and the step (II) is a step of activating surfaces of the first substrate and the second substrate by plasma treatment in a temperature range of 30 to 100°C. Step (I): preparing a first substrate having an (A-1) metal electrode and an exposed (B-1) resin layer exposed on the same surface of a substrate body, and a second substrate having an (A-2) metal electrode and an exposed (B-2) resin layer or (C) inorganic insulating layer exposed on the same surface of a substrate body; Step (II): activating the surfaces of the first substrate and the second substrate by plasma treatment or UV irradiation; Step (III): bonding the first substrate and the second substrate by direct bonding, with at least a portion of the (A-1) metal electrode and the (A-2) metal electrode and at least a portion of the (B-1) resin layer facing the (B-2) resin layer or the (C) inorganic insulating layer; [5] at least one of the (B-1) resin layer and the (B-2) resin layer is made of a cured product of a resin composition (D), and the resin composition (D) contains a resin (E) and a solvent, The method for producing a laminate according to any one of [1] to [4], wherein the resin (E) has either or both of a repeating unit represented by formula (1-A) and a repeating unit represented by formula (1-B), and further the resin (E) has either or both of a repeating unit represented by formula (1-C) and a repeating unit represented by formula (1-D), and when all repeating units contained in the resin (E) are taken as 100 mol %, the total of the repeating units represented by formula (1-A) and the repeating units represented by formula (1-B) in the resin (E) is 80 to 99 mol %, and the total of the repeating units represented by formula (1-C) and the repeating units represented by formula (1-D) in the resin (E) is 1 to 10 mol %.

[0017]

[0018] In formula (1-A), formula (1-B), formula (1-C) and formula (1-D), R １each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by formula (2). Each s independently represents an integer of 1 to 50. ８ and R ９ R each independently represents an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ４ ~R ７ each independently represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. Each X independently represents a group represented by formula (3), and each Y independently represents a group represented by formula (4).

[0019]

[0020] In formula (2), R １０ is an alkyl group having 1 to 5 carbon atoms, R １１ represents an alkylidene group having 1 to 5 carbon atoms. * represents a bonding site. In formula (3), n is an integer of 0 to 3, and m is an integer of 1 to 2. * represents a bonding site. In formula (4), R ２ and R ３ each independently represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a carboxy group, a sulfonic acid group, or a mercapto group. p is an integer of 0 to 4, q is an integer of 0 to 4, and r is an integer of 0 to 2. Z is a bond, atom, or group selected from a single bond, an alkylene group having 1 to 12 carbon atoms, a halogenated alkylene group having 1 to 12 carbon atoms, a sulfonyl group, an S atom, an O atom, a CO group, and a COO group. * represents a bonding site.

[0021] [6] The method for producing a laminate according to any one of [1] to [5], wherein in the step (III), the first substrate and the second substrate are bonded under a bonding pressure of 0.1 to 1.0 MPa.

[0022] [7] The method for producing a laminate according to any one of [1] to [6], wherein the average linear expansion coefficient of the cured product of the resin composition (D) in the temperature range of 50 to 150°C is 0 to 40 ppm / K.

[0023] [8] The method for producing a laminate according to any one of [1] to [7], wherein the step (I) includes a smoothing step using at least one of chemical mechanical polishing and surface planing.

[0024] [9] The method for manufacturing a laminate according to any one of [1] to [8], wherein in the step (III), when the first substrate and the second substrate are bonded, the temperature of the bonding stage and the temperature of the bonding head are both 250°C or less, and at least one of the temperature of the bonding stage and the temperature of the bonding head is 50°C or more.

[0025]

[10] The method for producing a laminate according to any one of [1] to [9], further comprising a step of performing an annealing treatment at a temperature of 150° C. or higher and 250° C. or lower after the step (III).

[0026]

[11] A resin composition comprising a resin (E) and a solvent, wherein the resin (E) has either or both of a repeating unit represented by formula (1-A) and a repeating unit represented by formula (1-B), and the resin (E) further has either or both of a repeating unit represented by formula (1-C) and a repeating unit represented by formula (1-D), and when all repeating units contained in the resin (E) are taken as 100 mol %, the total of the repeating units represented by formula (1-A) and the repeating units represented by formula (1-B) in the resin (E) is 80 to 99 mol %, and the total of the repeating units represented by formula (1-C) and the repeating units represented by formula (1-D) in the resin (E) is 1 to 10 mol %.

[0027]

[0028] In formula (1-A), formula (1-B), formula (1-C) and formula (1-D), R １ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by formula (2). Each s independently represents an integer of 1 to 50. ８ and R ９ R each independently represents an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ４ ~R７ each independently represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. Each X independently represents a group represented by formula (3), and each Y independently represents a group represented by formula (4).

[0029]

[0030] In formula (2), R １０ is an alkyl group having 1 to 5 carbon atoms, R １１ represents an alkylidene group having 1 to 5 carbon atoms. * represents a bonding site. In formula (3), n is an integer of 0 to 3, and m is an integer of 1 to 2. * represents a bonding site. In formula (4), R ２ and R ３ each independently represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a carboxy group, a sulfonic acid group, or a mercapto group. p is an integer of 0 to 4, q is an integer of 0 to 4, and r is an integer of 0 to 2. Z is a bond, atom, or group selected from a single bond, an alkylene group having 1 to 12 carbon atoms, a halogenated alkylene group having 1 to 12 carbon atoms, a sulfonyl group, an S atom, an O atom, a CO group, and a COO group. * represents a bonding site.

[0031]

[12] The resin composition according to

[11] , containing 0.1 to 3 parts by mass of a compound represented by formula (5) relative to 100 parts by mass of the resin (E).

[0032]

[0033] In formula (5), R １２ , R １３ , R １４ and R １５ each independently represents a group having 1 to 5 carbon atoms, 0 to 2 oxygen atoms, and 0 to 1 nitrogen atom, or a hydrogen atom.

[0034]

[13] The resin composition according to

[11] or

[12] , containing 0.001 to 3 parts by mass of N,N-dimethyl-3-(dimethylamino)propanamide per 100 parts by mass of the resin (E).

[0035]

[14] A cured product obtained by curing the resin composition according to any one of

[11] to

[13] .

[0036]

[15] A laminate comprising the cured product according to

[14] .

[0037]

[16] A semiconductor device comprising the laminate according to

[15] .

[0038] The present invention provides a resin composition that can provide a highly reliable laminate having a high adhesive strength between two substrates when they are bonded together, a cured product, a laminate including the cured product, a semiconductor device including the laminate, and a method for producing the laminate.

[0039] Schematic cross-sectional view of a laminate produced by a W2W process. Schematic cross-sectional view of a laminate produced by a C2W process. Schematic cross-sectional view showing a manufacturing process of a laminate using a W2W process. Schematic cross-sectional view showing a manufacturing process of a laminate using a C2W process.

[0040] <Definition> In the present invention, the term "repeating unit" refers to a regularly repeated chemical structural unit derived from the chemical structure of a monomer contained in a polymer compound. When the polymer compound is a polyimide or polyamic acid, the "repeating unit" refers to a structure in which a diamine corresponding to the monomer and a tetracarboxylic dianhydride or a derivative thereof, or a tetracarboxylic acid or a derivative thereof are bonded via an imide bond or an amide bond. When the polymer compound has a terminal-capped structure, a chemical structure in which an adjacent structure is a terminal-capped structure is included in the "repeating unit".

[0041] In the present invention, the numerical range indicated using "to" includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively.

[0042] The "cyclization rate" of the resin in the present invention is determined by measuring the infrared absorption spectrum of the cured product and determining the peak (1780 cm) derived from the imide structure. －１ Near 1377 cm －１The cyclization rate (imide ring closure rate) can be calculated from the intensity of the peak derived from the imide structure of the sample to be measured, with the intensity of the peak derived from the imide structure of the sample heat-treated at 350°C for 1 hour being taken as the peak intensity for a cyclization rate (imide ring closure rate) of 100%.

[0043] The "hybrid bonding" in the present invention is a technique in which at least one surface of a first substrate having an (A-1) metal electrode and an exposed (B-1) resin layer exposed on the same surface of the substrate body, and a second substrate having an (A-2) metal electrode and an exposed (B-2) resin layer or (C) inorganic insulating layer exposed on the same surface of the substrate body, is activated by plasma treatment or UV irradiation, and at least a portion of the (A-1) metal electrode faces the (A-2) metal electrode, and at least a portion of the (B-1) resin layer faces the (B-2) resin layer or the (C) inorganic insulating layer, and the first substrate and the second substrate are bonded by direct bonding.

[0044] Here, direct bonding means bonding two surfaces without using a bonding aid material such as an adhesive. For example, when bonding electrodes together, it is common to use a conductive bonding aid such as solder, but a bonding method that does not use a bonding aid is called direct bonding. Here, the (B-1) resin layer and the (B-2) resin layer are not present at the bonding interface between the electrodes in the laminate, and therefore do not qualify as adhesive aids. Furthermore, further steps not described here may be added.

[0045] <Resin Composition> The resin composition and the cured product of the resin composition according to the first aspect of the present invention will be described below. However, the present invention is not limited to the following embodiments, and various modifications can be made as long as the object of the invention can be achieved and the gist of the invention is not deviated from.

[0046] A resin composition according to a first aspect of the present invention comprises a resin (E) and a solvent, wherein the resin (E) has either or both of a repeating unit represented by formula (1-A) and a repeating unit represented by formula (1-B), and the resin (E) further has either or both of a repeating unit represented by formula (1-C) and a repeating unit represented by formula (1-D), and when the total amount of all repeating units contained in the resin (E) is taken as 100 mol %, the total amount of the repeating units represented by formula (1-A) and the repeating units represented by formula (1-B) in the resin (E) is 80 to 99 mol %, and the total amount of the repeating units represented by formula (1-C) and the repeating units represented by formula (1-D) in the resin (E) is 1 to 10 mol %.

[0047]

[0048] In formula (1-A), formula (1-B), formula (1-C) and formula (1-D), R １ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by formula (2). Each s independently represents an integer of 1 to 50. ８ and R ９ R each independently represents an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ４ ~R ７ each independently represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. Each X is independently any group represented by formula (3), and each Y is independently a group represented by formula (4). The above-mentioned substituents and structures may have a heteroatom, and may be either unsubstituted or substituted.

[0049]

[0050] In formula (2), R １０ is an alkyl group having 1 to 5 carbon atoms, R １１ represents an alkylidene group having 1 to 5 carbon atoms. * represents a bonding site. In formula (3), n is an integer of 0 to 3, and m is an integer of 1 to 2. * represents a bonding site. In formula (4), R ２ and R３ each independently represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a carboxy group, a sulfonic acid group, or a mercapto group. p is an integer from 0 to 4, q is an integer from 0 to 4, and r is an integer from 0 to 2. Z is a bond, atom, or group selected from a single bond, an alkylene group having 1 to 12 carbon atoms, a halogenated alkylene group having 1 to 12 carbon atoms, a sulfonyl group, an S atom, an O atom, a CO group, and a COO group. * represents a bonding site. The above-mentioned substituents and structures may have heteroatoms and may be either unsubstituted or substituted.

[0051] The resin composition of the present invention is preferably used to form a resin layer in hybrid bonding. By using a cured product of the resin composition of the present invention as a resin layer in hybrid bonding, a laminate having high adhesive strength and high reliability can be obtained. The reason for this is presumed to be as follows. However, the following presumption is not intended to limit the interpretation of the resin composition of the present invention, but is provided as an example.

[0052] Resin (E) in the resin composition of the present invention has either or both of repeating units represented by formula (1-A) and repeating units represented by formula (1-B), and further has either or both of repeating units represented by formula (1-C) and repeating units represented by formula (1-D), and when the total amount of repeating units contained in resin (E) is taken as 100 mol%, the sum of repeating units represented by formula (1-A) and repeating units represented by formula (1-B) in resin (E) is 80 to 99 mol%, and resin (E) has high rigidity. This rigidity is thought to reduce the difference in average linear expansion coefficient with the metal electrode during formation of a cured product, contribute to stress relaxation on the laminate, suppression of stress-induced cracking, and reduction of substrate warpage, thereby improving the reliability of the laminate.

[0053] Furthermore, resins with high rigidity increase the elastic modulus when a cured product is formed, which leads to a decrease in the amount of deformation caused by foreign matter at the bonding interface during hybrid bonding, and as a result, adhesive strength tends to decrease, making them generally difficult to apply. However, the resin (E) in the resin composition of the present invention contains a group having a siloxane bond in which a silicon atom is bonded to an alkylene group, an alkenylene group, an alkynylene group, or an arylene group. It is believed that by having this chemical structure, when the surface of the first or second substrate is activated by plasma treatment or UV treatment in hybrid bonding, the silanol groups generated by cleavage of the siloxane bond at a portion of the outermost surface have high reactivity, increasing the surface free energy of the bonding interface and enabling high adhesive strength to be obtained in direct bonding.

[0054] <Resin (E)> The resin (E) of the present invention will be described below. Resin (E) has either or both of a repeating unit represented by formula (1-A) and a repeating unit represented by formula (1-B), and further has either or both of a repeating unit represented by formula (1-C) and a repeating unit represented by formula (1-D), and when all repeating units contained in resin (E) are taken as 100 mol %, the total of the repeating units represented by formula (1-A) and the repeating units represented by formula (1-B) in resin (E) is 80 to 99 mol %, and the total of the repeating units represented by formula (1-C) and the repeating units represented by formula (1-D) in resin (E) is 1 to 10 mol %.

[0055] In formula (1-B) and formula (1-D), R １ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by formula (2), and from the viewpoint of suppressing metal migration, an alkyl group having 1 to 10 carbon atoms is preferred. As the alkyl group having 1 to 10 carbon atoms, a methyl group is preferred. In addition, since it is believed that hydroxyl groups are generated by plasma or UV treatment in hybrid bonding, which improves the bonding strength of the laminate, R １ are each independently a group represented by formula (2).

[0056] In formula (2), R １０ is an alkyl group having 1 to 5 carbon atoms, R １１ represents an alkylidene group having 1 to 5 carbon atoms. １０ A preferred example of R is a methyl group. １１ A preferred example of is a methylene group, but is not limited thereto.

[0057] In formula (1-C) and formula (1-D), each s is independently an integer of 1 to 50, and is preferably 1 from the viewpoint of film strength. In addition, from the viewpoint of adhesive strength of the laminate, it is also one of the preferred embodiments that each s is independently an integer of 2 to 50. ８ and R ９ are each independently an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an n-propylene group. ４ ~R ７ are each independently an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group, and are preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group.

[0058] In formula (1-A), formula (1-B), formula (1-C), and formula (1-D), X is each independently any group represented by formula (3). In formula (3), n is an integer of 0 to 3, and m is an integer of 1 or 2. From the viewpoint of reducing stress with the metal wiring, n is preferably 1, and m is preferably 0. When n is 1, X is a biphenyl group, and when m is 0, X is a phenyl group.

[0059] In formula (1-A) and formula (1-B), Y is each independently a group represented by formula (4). In formula (4), Z is a bond, atom, or group selected from a single bond, an alkylene group having 1 to 12 carbon atoms, a halogenated alkylene group having 1 to 12 carbon atoms, a sulfonyl group, an S atom, an O atom, a CO group, and a COO group. From the viewpoint of adhesion strength of hybrid bonding, when the total number of Z in resin (E) is 100 mol%, it is more preferable that 5 mol% to 90 mol% of Z are at least one or more groups selected from sulfonyl groups, S atoms, O atoms, CO groups, and COO groups, and when the total number of Z in resin (E) is 100 mol%, it is even more preferable that 20 mol% to 50 mol% of Z are O atoms. As a result, when surface activation is performed by plasma treatment or UV irradiation in hybrid bonding, it tends to become a source of hydroxyl groups and increase adhesive strength.

[0060] In formula (4), R ２ and R ３ are each independently an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a carboxy group, a sulfonic acid group, or a mercapto group. p is an integer of 0 to 4, q is an integer of 0 to 4, and r is an integer of 0 to 2. From the viewpoint of film strength, it is preferable that p and q are each 0. Furthermore, from the viewpoint of adhesive strength in hybrid bonding, it is preferable that p and q are 1 and R ２ and R ３ In one preferred embodiment, r is a methoxy group. From the viewpoint of adhesive strength in hybrid bonding, r is preferably 1 to 2. In addition, from the viewpoint of film strength, r is also preferably 0.

[0061] When all repeating units contained in the resin (E) of the present invention are taken as 100 mol%, the sum of the repeating units represented by formula (1-A) and the repeating units represented by formula (1-B) in the resin (E) is preferably 80 mol% or more, more preferably 85 mol% or more, and even more preferably 90 mol% or more, from the viewpoint of improving the reliability of the laminate. On the other hand, the sum of the repeating units represented by formula (1-A) and the repeating units represented by formula (1-B) in the resin (E) is preferably 99 mol% or less, more preferably 97 mol% or less, and even more preferably 95 mol% or less, from the viewpoint of improving the reliability and adhesive strength of the laminate.

[0062] When all repeating units contained in the resin (E) of the present invention are taken as 100 mol%, the sum of the repeating units represented by formula (1-C) and the repeating units represented by formula (1-D) in the resin (E) is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 4 mol% or more from the viewpoint of improving adhesive strength. On the other hand, the sum of the repeating units represented by formula (1-C) and the repeating units represented by formula (1-D) in the resin (E) is preferably 10 mol% or less, more preferably 8 mol% or less, and even more preferably 6 mol% or less from the viewpoint of improving the reliability and adhesive strength of the laminate.

[0063] The resin (E) of the present invention preferably has either or both of a repeating unit represented by formula (6-A) and a repeating unit represented by formula (6-B).

[0064] When all repeating units contained in the resin (E) of the present invention are taken as 100 mol%, the sum of the repeating units represented by formula (6-A) and the repeating units represented by formula (6-B) in the resin (E) is preferably 1 mol% or more, more preferably 3 mol% or more, from the viewpoint of improving film strength and suppressing outgassing. On the other hand, the sum of the repeating units represented by formula (6-A) and the repeating units represented by formula (6-B) in the resin (E) is preferably 18 mol% or less, more preferably 10 mol% or less, and even more preferably 5 mol% or less, from the viewpoint of improving film strength and suppressing outgassing.

[0065]

[0066] In formula (6-A) and formula (6-B), R １ and X are preferably R in formula (1-A), formula (1-B), formula (1-C) and formula (1-D). １ and X are the same as the preferred forms of X. In formula (6-A) and formula (6-B), W is each independently a group having 1 to 25 carbon atoms and having a heterocycle containing 2 to 4 nitrogen atoms, and W is preferably a group selected from formula (7). The above-mentioned substituents and structures may have a heteroatom, and may be either unsubstituted or substituted.

[0067]

[0068] In formula (7), R １６ , R １７ and R １８ Each of R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. * represents a bonding site. １６ , R １７ and R １８ are each more preferably independently a hydrogen atom or a methyl group. The above-mentioned substituents and structures may have heteroatoms, and may be either unsubstituted or substituted.

[0069] This tends to make it possible to obtain a cured product of a resin composition with a high cyclization rate, and also makes it possible to suppress the occurrence of degassing compared to when a curing accelerator is added to the resin composition.

[0070] Resin (E) of the present invention may contain repeating units other than those represented by formulas (1-A) to (1-D), (6-A) and (6-B) within the range that does not impair the properties. The repeating units other than those represented by formulas (1-A) to (1-D), (6-A) and (6-B) may be contained in an amount of 1 to 19 mol % when the total repeating units contained in the entire resin (E) is taken as 100 mol %.

[0071] <Resin Monomer> The resin (E) of the present invention may contain the following residues: In formulas (1-A), (1-B), (1-C), (1-D), (6-A), and (6-B), X represents a residue of 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, or a tetracarboxylic acid dianhydride, tetracarboxylic acid dichloride, or tetracarboxylic acid activated diester thereof, and among these, X is preferably a residue of 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid) or 3,3',4,4'-biphenyltetracarboxylic acid. In addition, from the viewpoint of adhesive strength, X is also preferably a residue of 2,3,3',4'-biphenyltetracarboxylic acid or 2,2',3,3'-biphenyltetracarboxylic acid. These residues may be contained in the resin alone or in combination of two or more.

[0072] In formula (1-A) and formula (1-B), Y is m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3-sulfonic acid-4,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)hexafluoropropane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone. Examples of the residues of Y include sulfide, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, dimercaptophenylenediamine, and 4-aminobenzoic acid 4-aminophenyl ester, and among these, Y is preferably a residue of p-phenylenediamine or 4,4'-diaminodiphenyl ether. In addition, from the viewpoint of adhesive strength, Y is also preferably a residue of 3,4'-diaminodiphenyl ether or 1,3-bis(3-aminophenoxy)benzene. These residues may be contained alone or in combination of two or more kinds in the resin.

[0073] The structures represented by formula (1-C) and formula (1-D) contain a diamine residue having a siloxane structure, and examples of the diamine residue having a siloxane structure include 1,3-bis(4-anilino)tetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, and X-22-9409 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), and DOWSIL (registered trademark) BY 16-853 U Silicone. Fluid (trade name, manufactured by Dow Toray Industries, Inc.), and the like. Among these, the diamine residue having a siloxane structure is preferably a residue of 1,3-bis(4-anilino)tetramethyldisiloxane or 1,3-bis(3-aminopropyl)tetramethyldisiloxane.

[0074] In formula (6-A) and formula (6-B), W is a group having 1 to 25 carbon atoms and a heterocyclic ring containing 2 to 4 nitrogen atoms, i.e., a diamine residue having 1 to 25 carbon atoms and a heterocyclic ring containing 2 to 4 nitrogen atoms. Examples of the diamine residue having 1 to 25 carbon atoms and a heterocyclic ring containing 2 to 4 nitrogen atoms include residues of 1H-1,2,4-triazole-3,5-diamine, 1H-1,3-imidazole-2,4-diamine, 4,40-((5-methylpyrimidine-2,4-diyl)bis(oxy))dianiline, and 4,40-((6-methylpyrimidine-2,4-diyl)bis(oxy))dianiline. Among these, the diamine residue having 1 to 25 carbon atoms and a heterocyclic ring containing 2 to 4 nitrogen atoms is preferably a residue of 1H-1,2,4-triazole-3,5-diamine.

[0075] When the resin (E) of the present invention has a repeating unit other than the repeating units represented by formulas (1-A) to (1-D), (6-A) and (6-B), examples of the residue of the tetracarboxylic acid anhydride constituting the repeating unit other than the repeating units represented by formulas (1-A) to (1-D), (6-A) and (6-B) include 2,2',3,3'-benzophenonetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenoxy) bis(2,3-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 2,2'-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, Examples of the tetracarboxylic acid include 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)]bis(3,4-dicarboxybenzoic acid amide), bicyclo[2.2.2]octan-7-ene-2,3,5,6-tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, and residues of their tetracarboxylic acid dianhydrides, tetracarboxylic acid dichlorides, or tetracarboxylic acid active diesters. These residues may be contained in the resin either alone or in combination of two or more.

[0076] Furthermore, it is preferable that the resin (E) has a residue of a tetracarboxylic acid or acid dianhydride having a siloxane structure, since direct bonding is possible at a low temperature of from room temperature to about 100° C. Examples of the acid dianhydride having a siloxane structure include residues of X-22-168AS, X-22-168A, X-22-168B, and X-22-168-P5-B.

[0077] Examples of diamine residues constituting repeating units other than those represented by formulas (1-A) to (1-D), (6-A) and (6-B) include bis(4-aminophenoxy)biphenyl, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 9,10-anthracenediamine, 4,4'-diaminobenzanilide, 3-carboxy-4,4'-diaminodiphenyl ether, bis[4-(4-aminophenoxy)phenyl]ether, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxy)phenyl, bis(4 ... 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(3-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-6-aminobenzoxazole, 2-(3-aminophenyl)-6-aminobenzoxazole, 1,4-bis(5-amino-2-benzoxazolyl)benzene, 1,4-bis(6-amino-2-benzoxazolyl)benzene, 1,3-bis(5-aminophenyl)sulfone, 2,7-diaminofluorene, 9,9-bis(4-aminophenyl)fluorene, ... bis(amino-2-benzoxazolyl)benzene, 1,3-bis(6-amino-2-benzoxazolyl)benzene, 2,6-bis(4-aminophenyl)benzobisoxazole, 2,6-bis(3-aminophenyl)benzobisoxazole, bis[(3-aminophenyl)-5-benzoxazolyl], bis[(4-aminophenyl)-5-benzoxazolyl], bis[(3-aminophenyl)-6-benzoxazolyl], bis[(4-aminophenyl)-6-benzoxazolyl], ethylenediamine, 1,3-diamino Examples of residues include residues of cyclohexanediamine, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, bis(4-aminocyclohexyl)methane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and dimer diamine. These residues may be contained in the resin either alone or in combination of two or more.

[0078] Furthermore, when a repeating unit other than the repeating units represented by formulas (1-A) to (1-D), (6-A), and (6-B) has a phenolic hydroxyl group, the adhesive strength at the time of bonding is improved and, when the metal electrode is copper or silver, corrosion can be reduced. Therefore, the repeating unit other than the repeating units represented by formulas (1-A) to (1-D), (6-A), and (6-B) may contain a residue of a bisaminophenol compound, as long as the properties are not impaired.Examples of the residue of a bisaminophenol compound include bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)methylene, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis(3-amino-4-hydroxyphenyl)sulfone, 2,2'-bis(3-amino-4-hydroxyphenyl)propane, 2,2'-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 9,9-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 9,9-bis[N-(4-aminobenzoyl)-3-amino- 4-hydroxyphenyl]fluorene, N,N'-bis(3-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4 bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, 3,3'-diamino-4,4'-biphenol, bis(3-amino-4-hydroxyphenyl)methane, 1,1-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane.

[0079] Furthermore, by capping the resin terminals with a monoamine, acid anhydride, acid chloride, or monocarboxylic acid, it is possible to adjust the weight-average molecular weight of resin (E) or introduce functional groups different from those in the molecule. Therefore, known monoamines, acid anhydrides, acid chlorides, or monocarboxylic acids may be used. The weight-average molecular weight of resin (E) is preferably 1,000 or more, more preferably 10,000 or more. On the other hand, the weight-average molecular weight of resin (E) is preferably 100,000 or less, more preferably 60,000 or less. The weight-average molecular weight (Mw) of resin (E) can be confirmed using a GPC (gel permeation chromatography) apparatus Waters 2690-996 (manufactured by Nihon Waters Co., Ltd.). The weight-average molecular weight (Mw) can be calculated in terms of polystyrene by measuring N-methyl-2-pyrrolidone as the developing solvent.

[0080] Examples of solvents used in the polymerization of resin (E) include, but are not limited to, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, amides such as N,N-dimethylisobutyric acid amide or methoxy-N,N-dimethylpropionamide, cyclic esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone or α-methyl-γ-butyrolactone, carbonates such as ethylene carbonate or propylene carbonate, glycols such as triethylene glycol, propylene glycol or propylene glycol monomethyl ether acetate, phenols such as m-cresol or p-cresol, acetophenone, sulfolane, dimethyl sulfoxide, tetrahydrofuran, or ethyl lactate.

[0081] <Solvent> The resin composition of the present invention contains a solvent. Examples of the solvent include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, N,N-dimethylisobutyric acid amide, and methoxy-N,N-dimethylpropionamide; ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone; esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons such as toluene and xylene. The resin composition may contain two or more of these.

[0082] From the viewpoint of suppressing outgassing from the cured product by strengthening the interaction with the resin, it is also a preferred embodiment to use a solvent with an HSP value of 17 to 18. Here, the HSP value is the Hansen solubility parameter calculated by the Stefanis-Panayiotou equation described in a non-patent document (Emmanuel Stefanis and Costas Panayiotou, Int J Thermophys (2008) 29:568-585). Also, from the viewpoint of reducing outgassing from the cured product, it is also a preferred embodiment to use a solvent with a boiling point of 180°C or less. The content of the solvent is preferably 100 parts by mass or more per 100 parts by mass of the resin (E) in order to dissolve the resin, and is preferably 1,500 parts by mass or less in order to form a coating film with a thickness of 1 μm or more.

[0083] <Curing Accelerator> The resin composition of the present invention preferably further contains a curing accelerator. Hybrid bonding is also expected to be applied to the manufacture of devices sensitive to thermal history, and the manufacturing process is preferably carried out at a low temperature of 250°C or less. The inclusion of a curing accelerator enables high imidization by forming a cured product at a temperature of 250°C or less. It is believed that the reduction in the proportion of carboxylic acid in the resin can suppress metal ion migration, and that the resulting high film properties can result in a highly reliable cured product, as well as suppressing a decrease in adhesive strength due to the generation of voids at the adhesive interface caused by degassing during hybrid bonding.

[0084] Furthermore, when the cyclization rate of the cured resin composition is high, the adhesive strength of the laminate produced by hybrid bonding tends to decrease, as described in Japanese Patent No. 7354479. However, by applying the resin composition of the present invention containing a resin having a siloxane bond, it is believed that hybrid bonding with high adhesive strength can be achieved by using a cured product with a high cyclization rate in the resin layer.

[0085] The resin composition of the present invention may further contain, as a curing accelerator, imidazole, pyrazole, triazole, tetrazole, benzimidazole, naphthoimidazole, indazole, benzotriazole, purine, imidazoline, pyrazoline, pyridine, quinoline, isoquinoline, dipyridyl, diquinolyl, pyridazine, pyrimidine, pyrazine, phthalazine, quinoxaline, quinazoline, cinnoline, naphthyridine, acridine, phenanthridine, benzoquinoline, benzoisoquinoline, benzocinnoline, benzophthalazine, benzoquinoxaline, benzoquinazoline, phenanthroline, or phenazine The resin composition may contain, but is not limited to, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, oxadiazole, thiadiazole, pyrroledione, isoindoledione, pyrrolidinedione, benzisoquinolinedione, triethylenediamine, or hexamethylenetetramine, or compounds in which some of the hydrogen atoms in the aromatic rings, heterocycles, or hydrocarbons or hydrogen nitrides thereof have been substituted with groups having 6 or less carbon atoms. The resin composition may contain two or more of these.

[0086] The resin composition of the present invention preferably contains a compound represented by formula (5) as a curing accelerator.

[0087]

[0088] In formula (5), R １２ , R １３ , R １４ and R １５ each independently represents a group having 1 to 5 carbon atoms, 0 to 2 oxygen atoms, and 0 to 1 nitrogen atom, or a hydrogen atom.

[0089] Examples of the group having 1 to 5 carbon atoms, 0 to 2 oxygen atoms, and 0 to 1 nitrogen atoms include a methyl group, an ethyl group, a propyl group, a methoxycarbonylaminomethyl group, a methoxycarbonylaminoethyl group, an aminoethyl group, an aminopropyl group, etc. The above-mentioned substituents and structures may have heteroatoms, and may be either unsubstituted or substituted.

[0090] The resin composition of the present invention preferably contains 0.1 to 3 parts by mass of the compound represented by formula (5) per 100 parts by mass of the resin (E).

[0091] Examples of compounds represented by formula (5) include 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 1-methyl-4-ethylimidazole, 1-methoxycarbonylaminomethylimidazole, 1-(2-methoxycarbonylaminoethyl)-2-methylimidazole, 1-(2-aminoethyl)-2-methylimidazole, and 1-(3-aminopropyl)-2-methylimidazole. By including a compound represented by formula (5) in the resin composition, a sufficient curing acceleration effect can be obtained at curing temperatures of 200°C or less, which is expected for hybrid bonding applications. Furthermore, the boiling point of the curing accelerator is preferably 100°C to 200°C, and more preferably 120°C to 180°C. Within this range, the effect as a curing accelerator is exhibited, and the amount of outgassing during hybrid bonding can be suppressed.

[0092] From the viewpoint of suppressing metal ion migration and suppressing the amount of outgassing, the content of the curing accelerator is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more, per 100 parts by mass of the resin (E). On the other hand, from the viewpoint of improving the storage stability of the resin composition, the content of the curing accelerator is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of the resin (E). Within this range, the effect of the additive can be obtained, the storage stability of the resin composition is excellent, and the amount of outgassing from the cured product in hybrid bonding can be suppressed.

[0093] <Silane Coupling Agent> The resin composition of the present invention preferably further contains a silane coupling agent. The resin composition of the present invention preferably contains, as the silane coupling agent, a silane coupling agent such as 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyltrimethoxysilane, or 3-mercaptopropyltrimethoxysilane. The silane coupling agent is preferably contained in an amount that does not impair the storage stability of the resin composition of the present invention.

[0094] By including a silane coupling agent, silanol groups are generated by plasma or UV treatment in hybrid bonding, and the high reactivity tends to increase the adhesive strength of the laminate.

[0095] The content of the silane coupling agent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 1 part by mass or more, relative to 100 parts by mass of the resin (E) from the viewpoint of improving the bonding strength and improving the adhesion to the base substrate. On the other hand, the content of the silane coupling agent is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, relative to 100 parts by mass of the resin (E) from the viewpoint of improving the bonding strength and suppressing the generation of degassing.

[0096] Normally, silane coupling agents are a cause of outgassing, but by mixing them with the resin having a siloxane bond in the present invention, it is thought that they can interact with the silanol groups generated during hybrid bonding, forming covalent bonds and thereby suppressing outgassing.

[0097] <Crosslinking Agent> The resin composition of the present invention preferably further contains a crosslinking agent. The crosslinking agent preferably has a methylol group or an alkoxymethyl group. The number of methylol groups or alkoxymethyl groups contained in the crosslinking agent is preferably 2 or more, more preferably 3 or more. It is believed that the presence of these groups generates hydroxyl groups during the surface activation step by plasma or UV treatment in hybrid bonding, which leads to an increase in surface free energy and an increase in bonding strength.

[0098] Examples of crosslinking agents include, but are not limited to, MX-290, NIKALAC (registered trademark) MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, and NIKALAC MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.), and the following crosslinking agents. Two or more of these may be contained.

[0099] From the viewpoint of improving bonding strength, the content of the crosslinking agent is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 5 parts by mass or more, relative to 100 parts by mass of the resin (E). On the other hand, from the viewpoint of improving bonding strength, the content of the crosslinking agent is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, relative to 100 parts by mass of the resin (E).

[0100] <Antioxidant> The resin composition of the present invention preferably further contains an antioxidant. When the resin composition contains an antioxidant, it is possible to suppress oxidative degradation of the resin to be mixed. In addition, due to its rust-preventing effect on metal materials, it is possible to suppress metal oxidation caused by external moisture and the resulting decrease in adhesion and peeling. It is presumed that these effects improve the long-term reliability of the laminate.

[0101] The antioxidant is preferably a hindered phenol-based antioxidant or a hindered amine-based antioxidant. The number of phenol groups or amino groups in one molecule is preferably 2 or more, more preferably 4 or more, because this makes it easier to obtain an antioxidant effect. Addition of an antioxidant with this structure can improve the mechanical properties of the cured product after reliability tests such as high-temperature storage tests, and can suppress peeling from metal materials.

[0102] From the viewpoint of improving the reliability of the laminate, the content of the antioxidant is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of the resin (E). On the other hand, from the viewpoint of improving the reliability of the laminate, the content of the antioxidant is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less, per 100 parts by mass of the resin (E).

[0103] <Photosensitizer> The resin composition of the present invention preferably further contains a photosensitizer. By incorporating a photosensitizer into the resin composition, the resin composition can be made photosensitive. Forming a resin layer using a photosensitive resin composition simplifies the manufacturing method for the first substrate and the second substrate, and the photosensitizer can promote the reaction of the crosslinker, thereby enabling control of the elastic modulus. When imparting photosensitivity to a resin composition, a positive or negative photosensitizer is preferred. As the photosensitizer, a photopolymerization initiator or a photoacid generator is preferred. Among these, a material containing a photoacid generator is preferred from the standpoint of resolution. When imparting positive photosensitivity to a resin composition, a photoacid generator is preferred, and a naphthoquinone diazide compound is more preferred. Specific examples of photopolymerization initiators and photoacid generators include those described in JP 2018-165819 A. Preferred examples are also similar. The preferred content of the photosensitizer is 0.1 to 20 parts by mass per 100 parts by mass of the resin (E).

[0104] <Degassing Inhibitor> The resin composition of the present invention preferably further contains a degassing inhibitor. As the degassing inhibitor in the present invention, N,N-dimethyl-3-(dimethylamino)propanamide is preferred. By including the degassing inhibitor, degassing can be suppressed. The reason for this is presumed to be that the degassing inhibitor interacts with the low molecular weight components to suppress gasification of the low molecular weight components.

[0105] In the resin composition of the present invention, N,N-dimethyl-3-(dimethylamino)propanamide is preferably contained in an amount of 0.001 to 3 parts by mass per 100 parts by mass of resin (E). From the viewpoint of suppressing the amount of outgassing and improving the reliability of the laminate, the content of the degassing inhibitor is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, even more preferably 0.05 parts by mass or more, and particularly preferably 0.1 parts by mass or more per 100 parts by mass of resin (E). On the other hand, from the viewpoint of improving the reliability of the laminate, the content of the degassing inhibitor is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less per 100 parts by mass of resin (E).

[0106] Furthermore, the content of the degassing inhibitor in the resin composition of the present invention is more preferably 0.1 to 300 parts by mass relative to 100 parts by mass of the curing accelerator. From the viewpoint of suppressing the amount of degassing and improving the reliability of the laminate, the content of the degassing inhibitor is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, even more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more relative to 100 parts by mass of the curing accelerator. On the other hand, from the viewpoint of improving the reliability of the laminate, the content of the degassing inhibitor is preferably 300 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less relative to 100 parts by mass of the curing accelerator.

[0107] <Optional Resin> The resin composition of the present invention may contain an optional resin in addition to the resin (E) as long as the properties are not impaired. Examples of the optional resin include polysiloxane, acrylic polymer, epoxy resin, novolac resin, polybenzoxazole, and polybenzoxazole precursor. The content of the optional resin is preferably 0.1 to 20 parts by mass per 100 parts by mass of the resin (E).

[0108] <Cured Product and Physical Properties of the Cured Product> The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The cured product in the present invention can be obtained by applying the resin composition to a substrate body by a known method such as spin coating, slit die coating, spray coating, or inkjet coating, and then drying the coating film by heating with a hot plate, an oven, or infrared rays, and refers to a film in which, after the drying process, the cyclization rate of resin (E) in the resin composition has reached 50% or more and the solvent content relative to the mass of the entire cured product has reached 5% by mass or less.

[0109] The thickness of the film applied to the substrate is preferably 0.5 to 15 μm, more preferably 1 to 10 μm. In the case of a sheet, it can be formed by lamination. Furthermore, a drying process may be similarly performed after lamination. Furthermore, as long as the properties are not impaired, the film may be cured by at least one heat treatment, as necessary. When curing by heat, the curing temperature can be appropriately selected from a temperature range of 100°C to 400°C, and the curing time can be selected from 3 minutes to 3 hours depending on the purpose. Curing at 150°C to 250°C is preferred, and curing at 180°C to 220°C is even more preferred. Within this range, the burden on the substrate body is reduced, and the amount of outgassing during hybrid bonding is suppressed, resulting in a high resin cyclization rate, which tends to result in a highly reliable laminate. Furthermore, if the resin composition is photosensitive, a pattern such as a via hole may be formed in the cured product through exposure and development processes as needed.

[0110] The cyclization rate of the resin (E) in the cured product is preferably greater than 90%, more preferably 92% or more, and even more preferably 95% or more. On the other hand, the cyclization rate of the resin (E) in the cured product is preferably 100% or less. This can suppress metal ion migration between the cured product and the metal electrode, improving the reliability of the resulting laminate. When the cyclization rate of the cured product of the resin composition is high, the adhesive strength of the laminate produced by hybrid bonding tends to decrease. However, by using a cured product of the resin composition containing a resin having a siloxane bond in the present invention, it is believed that hybrid bonding with high adhesive strength can be achieved by using a cured product with a high cyclization rate in the resin layer. As mentioned above, it is preferable that the cyclization rate is such that the imide ring closure rate is within the above range.

[0111] The average linear expansion coefficient of the cured product in the temperature range of 50 to 150°C is preferably 0 ppm / K or more, more preferably 15 ppm / K or more, and even more preferably 17 ppm / K or more. Meanwhile, the average linear expansion coefficient of the cured product in the temperature range of 50 to 150°C is preferably 40 ppm / K or less, more preferably 30 ppm / K or less, and even more preferably 25 ppm / K or less. A value within this range reduces the difference in linear expansion coefficient with copper, making it easier to ensure the reliability of the laminate after bonding. Here, "average linear expansion coefficient in the temperature range of 50 to 150°C" refers to the slope of a linear function obtained by approximating the linear expansion amount measured in the temperature range from a measurement start temperature of 50°C to a measurement end temperature of 150°C using the least squares method. It is preferable that the average linear expansion coefficient of the cured product in the temperature range of 50 to 150°C measured by thermomechanical analysis is within the above range.

[0112] As a method for adjusting the average linear expansion coefficient of the cured product, generally, increasing the proportion of repeating units having a rigid chemical structure such as phenyl groups or biphenyl groups in the resin tends to decrease the average linear expansion coefficient, while decreasing the proportion of repeating units having a rigid chemical structure such as phenyl groups or biphenyl groups in the resin tends to increase the average linear expansion coefficient. One example of a method for adjusting the average linear expansion coefficient of the cured product to 0 ppm / K or more and 40 ppm / K or less in the temperature range of 50 to 150°C is to adjust the proportion of repeating units having a rigid chemical structure such as phenyl groups or biphenyl groups in the resin (E) to 80 mol% or more, when all repeating units in the resin (E) in the cured product are 100 mol%.

[0113] The elastic modulus of the cured product is preferably 1.5 GPa or more, more preferably 2.0 GPa or more, and even more preferably 2.5 GPa or more. On the other hand, the elastic modulus of the cured product is preferably 7.0 GPa or less, more preferably 5.0 GPa or less, and even more preferably 3.5 GPa or less. By being in such a range, it becomes easier to obtain high adhesive strength and reliability while suppressing the generation of voids due to minute foreign matter during dicing. The elastic modulus of the cured product is determined by the method described in the examples.

[0114] As a method for adjusting the elastic modulus of the cured product, generally, increasing the ratio of repeating units having a rigid chemical structure such as a phenyl group or a biphenyl group in the resin tends to increase the elastic modulus, while decreasing the ratio of repeating units having a rigid chemical structure such as a phenyl group or a biphenyl group in the resin tends to decrease the elastic modulus. One example of a method for adjusting the elastic modulus of the cured product to 1.5 GPa or more and 7.0 GPa or less is to adjust the ratio of repeating units having a rigid chemical structure such as a phenyl group or a biphenyl group in the resin (E) to 80 mol% or more, when all repeating units in the resin (E) in the cured product are 100 mol%.

[0115] <Method for producing a laminate> Hereinafter, a description will be given of the methods for producing a laminate according to the second and third aspects of the present invention, as well as the laminate and semiconductor device obtained by the laminate production method. Note that when referring to the method for producing a laminate according to the present invention, this description is common to the methods for producing a laminate according to the second and third aspects of the present invention. On the other hand, when describing a method for producing a laminate according to a specific aspect, it will be referred to as the method for producing a laminate according to the second aspect of the present invention. Furthermore, the description regarding the method for producing a laminate is also common to the method for producing a laminate using a cured product of a resin composition according to the first aspect of the present invention. However, the present invention is not limited to the following embodiments, and various modifications are naturally possible within the scope that can achieve the object of the invention and do not deviate from the gist of the invention.

[0116] A second aspect of the present invention is a method for producing a laminate, comprising steps (I), (II), and (III) in this order, wherein at least one of the (B-1) resin layer and the (B-2) resin layer is made of a cured product of a resin composition (D), and the resin composition (D) contains a resin (E) and a solvent, and the resin (E) has either or both of a repeating unit represented by formula (1-A) and a repeating unit represented by formula (1-B), and the resin (E) further has either or both of a repeating unit represented by formula (1-C) and a repeating unit represented by formula (1-D), and when all repeating units contained in the resin (E) are taken as 100 mol %, the total of the repeating units represented by formula (1-A) and the repeating units represented by formula (1-B) in the resin (E) is 80 to 99 mol %, and the total of the repeating units represented by formula (1-C) and the repeating units represented by formula (1-D) in the resin (E) is 1 to 10 mol %. Step (I): preparing a first substrate having an (A-1) metal electrode and an exposed (B-1) resin layer on the same surface of the substrate body, and a second substrate having an (A-2) metal electrode and an exposed (B-2) resin layer or (C) inorganic insulating layer on the same surface of the substrate body; Step (II): activating the surfaces of the first substrate and the second substrate by plasma treatment or UV irradiation; Step (III): bonding the first substrate and the second substrate by direct bonding, with at least a portion of the (A-1) metal electrode and the (A-2) metal electrode and at least a portion of the (B-1) resin layer facing the (B-2) resin layer or the (C) inorganic insulating layer.

[0117]

[0118] In formula (1-A), formula (1-B), formula (1-C) and formula (1-D), R １ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by formula (2). Each s independently represents an integer of 1 to 50. ８ and R ９ R each independently represents an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms.４ ~R ７ each independently represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. Each X is independently any group represented by formula (3), and each Y is independently a group represented by formula (4). The above-mentioned substituents and structures may have a heteroatom, and may be either unsubstituted or substituted.

[0119]

[0120] In formula (2), R １０ is an alkyl group having 1 to 5 carbon atoms, R １１ represents an alkylidene group having 1 to 5 carbon atoms. * represents a bonding site. In formula (3), n is an integer of 0 to 3, and m is an integer of 1 to 2. * represents a bonding site. In formula (4), R ２ and R ３ each independently represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a carboxy group, a sulfonic acid group, or a mercapto group. p is an integer from 0 to 4, q is an integer from 0 to 4, and r is an integer from 0 to 2. Z is a bond, atom, or group selected from a single bond, an alkylene group having 1 to 12 carbon atoms, a halogenated alkylene group having 1 to 12 carbon atoms, a sulfonyl group, an S atom, an O atom, a CO group, and a COO group. * represents a bonding site. The above-mentioned substituents and structures may have heteroatoms and may be either unsubstituted or substituted.

[0121] A third aspect of the present invention is a method for producing a laminate, which comprises steps (I), (II), and (III) in this order, wherein at least one of the (B-1) resin layer and the (B-2) resin layer has an average linear expansion coefficient of 0 to 40 ppm / K in a temperature range of 50 to 150°C, and the step (II) is a step of activating surfaces of the first substrate and the second substrate by plasma treatment at a temperature of 30 to 100°C. Step (I): preparing a first substrate having an (A-1) metal electrode and an exposed (B-1) resin layer on the same surface of the substrate body, and a second substrate having an (A-2) metal electrode and an exposed (B-2) resin layer or (C) inorganic insulating layer on the same surface of the substrate body; Step (II): activating the surfaces of the first substrate and the second substrate by plasma treatment or UV irradiation; Step (III): bonding the first substrate and the second substrate by direct bonding, with at least a portion of the (A-1) metal electrode and the (A-2) metal electrode and at least a portion of the (B-1) resin layer facing the (B-2) resin layer or the (C) inorganic insulating layer.

[0122] In a third aspect of the present invention, there is provided a method for producing a laminate, wherein at least one of the (B-1) resin layer and the (B-2) resin layer comprises a cured product of a resin composition (D), and the resin composition (D) contains a resin (E) and a solvent, and the resin (E) has either or both of a repeating unit represented by the formula (1-A) and a repeating unit represented by the formula (1-B), and the resin (E) further has either or both of a repeating unit represented by the formula (1-C) and a repeating unit represented by the formula (1-D), and when all repeating units contained in the resin (E) are taken as 100 mol %, it is preferred that the total of the repeating units represented by the formula (1-A) and the repeating units represented by the formula (1-B) in the resin (E) is 80 to 99 mol %, and the total of the repeating units represented by the formula (1-C) and the repeating units represented by the formula (1-D) in the resin (E) is 1 to 10 mol %.

[0123] <Physical property values ​​of the cured product of resin composition (D), (B-1) resin layer, and (B-2) resin layer> In the method for producing a laminate of the present invention, the resin composition (D) is the same as the "resin composition" described above. Furthermore, in the method for producing a laminate of the present invention, examples and preferred descriptions of the resin (E), solvent, and other components contained in the resin composition (D) are the same as the examples and preferred descriptions of the resin composition of the present invention described above.

[0124] In step (I), when the total repeating units contained in the resin (E) in the cured product of the resin composition (D) is taken as 100 mol%, it is preferable that the sum of the repeating units represented by the above formula (1-A) and the repeating units represented by the above formula (1-B) in the resin (E) is 80 to 99 mol%, and the sum of the repeating units represented by the above formula (1-C) and the repeating units represented by the above formula (1-D) in the resin (E) is 1 to 10 mol%. Also in step (I), when the total repeating units contained in the resin (E) contained in at least one of the (B-1) resin layer and the (B-2) resin layer is taken as 100 mol%, it is preferable that the sum of the repeating units represented by the above formula (1-A) and the repeating units represented by the above formula (1-B) in the resin (E) is 80 to 99 mol%, and the sum of the repeating units represented by the above formula (1-C) and the repeating units represented by the above formula (1-D) in the resin (E) is 1 to 10 mol%. Hereinafter, when the content ratios of the repeating units represented by the formulas (1-A), (1-B), (1-C), and (1-D) in the resin (E) are within the above ranges, it may be referred to as "the resin (E) satisfies the conditions for the content ratios of repeating units of specific structures."

[0125] In step (I), the content ratios of the repeating units represented by formula (1-A), formula (1-B), formula (1-C), and formula (1-D) in resin (E) being within the above ranges refers to the state after step (I). Examples and preferred descriptions regarding the content ratios of these repeating units in resin (E) are the same as the examples and preferred descriptions for the repeating units in resin (E) contained in the resin composition of the present invention.

[0126] In step (I), the cyclization rate of resin (E) in the cured product of resin composition (D) is preferably greater than 90% and less than 100%. Furthermore, the cyclization rate of resin (E) contained in at least one of the (B-1) resin layer and the (B-2) resin layer is preferably greater than 90% and less than 100%. In step (I), the cyclization rate of resin (E) being within the above range refers to the state after step (I). These examples and preferred descriptions regarding the cyclization rate of resin (E) are the same as the examples and preferred descriptions regarding the cyclization rate of resin (E) in the cured product of the present invention.

[0127] In step (I), the average linear expansion coefficient of the cured product of resin composition (D) in the temperature range of 50 to 150°C is preferably 0 to 40 ppm / K. Also, in step (I), the average linear expansion coefficient of at least one of the (B-1) resin layer and the (B-2) resin layer in the temperature range of 50 to 150°C is preferably 0 to 40 ppm / K. Hereinafter, the average linear expansion coefficient of the cured product of resin composition (D), or the average linear expansion coefficient of at least one of the (B-1) resin layer and the (B-2) resin layer, being within the above range may be referred to as "the cured product of resin composition (D) satisfies the condition of an average linear expansion coefficient in a specific range" or "at least one of the (B-1) resin layer and the (B-2) resin layer satisfies the condition of an average linear expansion coefficient in a specific range". In step (I), the average linear expansion coefficient of the cured product of the resin composition (D) and the average linear expansion coefficient of at least one of the (B-1) resin layer and the (B-2) resin layer being within the above range refers to the state after step (I). Examples and preferred descriptions regarding these average linear expansion coefficients are the same as the examples and preferred descriptions regarding the average linear expansion coefficient of the cured product of the present invention described above.

[0128] When the step (II) described below is a step of activating the surfaces of the first substrate and the second substrate by plasma treatment in a temperature range of 30 to 100°C, from the viewpoint of improving the bonding strength and the reliability of the laminate, it is preferable that the average linear expansion coefficient of the cured product of the resin composition (D) in the temperature range of 50 to 150°C in the step (I) is 0 to 40 ppm / K.

[0129] Furthermore, when the step (II) described below is a step of activating the surfaces of the first substrate and the second substrate by plasma treatment in a temperature range of 30 to 100°C, from the viewpoint of improving the bonding strength and the reliability of the laminate, it is preferable that in the step (I), at least one of the (B-1) resin layer and the (B-2) resin layer has an average linear expansion coefficient of 0 to 40 ppm / K in a temperature range of 50 to 150°C.

[0130] The methods for adjusting the average linear expansion coefficient of the cured product of the resin composition (D) and the average linear expansion coefficient of at least one of the (B-1) resin layer and the (B-2) resin layer are the same as the methods for adjusting the average linear expansion coefficient of the cured product of the present invention.

[0131] In step (I), the elastic modulus of the cured product of resin composition (D) is preferably 1.5 to 7.0 GPa. Also, in step (I), the elastic modulus of at least one of the (B-1) resin layer and the (B-2) resin layer is preferably 1.5 to 7.0 GPa. In step (I), the elastic modulus of the cured product of resin composition (D) and the elastic modulus of at least one of the (B-1) resin layer and the (B-2) resin layer being within the above range refers to the state after step (I). Examples and preferred descriptions regarding these elastic moduli are the same as the examples and preferred descriptions regarding the elastic modulus of the cured product of the present invention described above. The methods for adjusting the elastic modulus of the cured product of resin composition (D) and the elastic modulus of at least one of the (B-1) resin layer and the (B-2) resin layer are the same as the methods for adjusting the elastic modulus of the cured product of the present invention described above.

[0132] Hereinafter, the (A-1) metal electrode and the (A-2) metal electrode may be collectively referred to as "(A) metal electrode," and the (B-1) resin layer and the (B-2) resin layer may be collectively referred to as "(B) resin layer."

[0133] <Step (I): Step of Preparing First Substrate and Second Substrate> The method for producing a laminate of the present invention includes the following step (I): Step (I): preparing a first substrate having an exposed metal electrode (A-1) and an exposed resin layer (B-1) on the same surface of a substrate main body, and a second substrate having an exposed metal electrode (A-2) and an exposed resin layer (B-2) or inorganic insulating layer (C) on the same surface of the substrate main body.

[0134] Details of step (I) will be explained using a specific example. In step (I), a substrate body is prepared. Here, the substrate body refers to a plate-shaped article, and the substrate body preferably contains one or more materials selected from the group consisting of silicon, lithium niobate, lithium tantalate, gallium nitride, silicon carbide, gallium arsenide, and indium phosphide. Among these, silicon is preferably used for the substrate body in applications involving semiconductor devices having functions such as arithmetic processing, information storage, or power control. By forming (A) a metal electrode and (B) a resin layer on the substrate body and then performing a smoothing process, a first substrate and a second substrate having (A) a metal electrode and (B) a resin layer are obtained. Furthermore, the first substrate and the second substrate before the laminate is manufactured can be substrates on which at least one of passive component and active component circuits is formed. By using such a substrate body, the resulting laminate functions as a semiconductor.

[0135] This section describes a case where an (A) metal electrode is formed first, followed by the formation of a (B) resin layer. The (A) metal electrode can be formed by a known method. Examples of methods for forming the (A) metal electrode include a subtractive method and a semi-additive method. The formation of a copper electrode by a semi-additive method will be described as a specific example. A seed layer of Ti, Ni, or the like is formed on the substrate body by sputtering, followed by patterning of a dry film resist, followed by electrolytic plating to form a copper electrode pattern, followed by the steps of removing the resist and then removing the seed layer. Then, by forming a (B) resin layer by the above-described method for forming a cured product, a substrate is obtained in which the exposed (A) metal electrode and the exposed (B) resin layer are provided on the same surface of the substrate body.

[0136] Next, a case where a (B) resin layer is formed first and then an (A) metal electrode is formed will be described. When a photosensitive resin composition (D) is used to form the (B) resin layer, the (B) resin layer can be formed by a method for forming a pattern in the case where the (B) resin layer has photosensitivity, among the above-mentioned methods for forming a cured product. When a resin composition (D) that does not have photosensitivity is used to form the (B) resin layer, the (B) resin layer can be formed by forming a cured product using the above-mentioned method for forming a cured product, and then patterning the cured product using a known method. Examples of patterning the cured product include a method in which a dry film resist is patterned on the cured product, a portion of the cured product is removed by dry etching, and then the dry film resist is removed. Thereafter, a seed layer of Ti, Ni, or the like that will form the (A) metal electrode is formed by sputtering, and an electrode pattern is formed using a known electrode material such as copper by electroplating, thereby obtaining the (A) metal electrode.

[0137] Next, a smoothing step is performed on the (A) metal electrode and the (B) resin layer to expose the (A) metal electrode and the (B) resin layer. A known method can be used for the smoothing step. The smoothing step preferably uses at least one of chemical mechanical polishing (CMP) and surface planing. That is, step (I) preferably includes a smoothing step using at least one of chemical mechanical polishing and surface planing.

[0138] Known methods can be used for CMP, and CMP is preferred because it can reduce surface roughness and increase bonding strength. Surface planing can be performed using, for example, a diamond bit, and using a surface planer can shorten the time required for the smoothing process. Furthermore, a process of performing CMP after surface planing is preferred because it can increase bonding strength and shorten the time required for the smoothing process. By performing the above smoothing process, a first substrate and a second substrate can be obtained, each having (A) a metal electrode and (B) a resin layer exposed on the same surface of the substrate body.

[0139] Next, a method for obtaining a second substrate having an exposed (A-2) metal electrode and an exposed (C) inorganic insulating layer on the same surface of the substrate body will be described. The second substrate having an exposed (A-2) metal electrode and an exposed (C) inorganic insulating layer on the same surface of the substrate body can be manufactured using known techniques (e.g., Materials 2022, 15(5), 1888). As a specific example of the manufacturing method, first, a silicon oxide film (SiO ) is formed as the (C) inorganic insulating layer on the substrate body by a method such as thermal oxidation, wet oxidation, sputtering, or CVD. ２ ) is formed. Next, patterning using a dry film resist, etching, and resist removal are performed. Thereafter, an electrode pattern is formed by electrolytic plating, and after the same smoothing process as described above, a second substrate can be obtained on the same surface with a silicon oxide film (C) as an inorganic insulating layer and an exposed metal electrode (A-2).

[0140] (C) The material of the inorganic insulating layer is SiO ２ (C) The inorganic insulating layer is SiO ２ A part or all of the above may be replaced with a silicon nitride film (SiN film) or a silicon carbonitride film (SiCN film).

[0141] Furthermore, at least one of the first substrate and the second substrate before the laminate is manufactured may be thinned by polishing the substrate body from the surface opposite to the surface having the (A) metal electrode and the (B) resin layer, or the (A) metal electrode and the (C) inorganic insulating layer, by a known method such as back grinding, if necessary. Furthermore, at least one of the first substrate and the second substrate before the laminate is manufactured may be processed into the shape of individual pieces (chips) by a known method such as dicing, if necessary.

[0142] <Step (II): Step of Activating the Surfaces of the First Substrate and the Second Substrate> The method for producing a laminate of the present invention includes the following step (II): Step (II): Activating the surfaces of the first substrate and the second substrate by plasma treatment or UV irradiation.

[0143] Details of step (II) will be explained using a specific example. The surfaces of the first substrate and the second substrate having (A) the metal electrode and (B) the resin layer, or (A) the metal electrode and (C) the inorganic insulating layer, are surface-activated by plasma treatment or UV irradiation. Among surface activation methods, activation by plasma treatment is preferred. Surface activation can increase the bonding strength.

[0144] The plasma treatment is performed using an inert gas as the plasma, with an oxygen volume concentration of preferably 1% or less, more preferably 0.1% or less, and even more preferably 0.01% or less. By setting the oxygen volume concentration to 1% or less, oxidation of the outermost metal electrode can be suppressed, electrical conductivity can be maintained, and oxidation of the resin layer can be suppressed, thereby suppressing a decrease in bonding strength. Examples of inert gases used in the plasma treatment include argon, helium, and nitrogen. From the viewpoint of maintaining the activated state after treatment for a long period of time, it is preferable to use helium as the inert gas to be converted into plasma. Because helium has low activation energy, the excited state of the resin layer activated by helium plasma is low and relatively stable. Therefore, since the activated state of the resin layer is maintained for a long period of time, the process tolerance regarding the waiting time from plasma treatment to direct bonding is increased, thereby improving process margins. Furthermore, the inert gas used in the plasma treatment may be a mixed gas containing two or more gases, or an active gas may be mixed. An example of an active gas to be mixed with the inert gas used in the plasma treatment is hydrogen. The plasma treatment is preferably carried out with an output in the range of 40 to 600 W, and the plasma irradiation time in the plasma treatment is preferably 10 to 200 seconds.

[0145] An example of a helium-containing plasma treatment for direct bonding is shown in a presentation such as "Atmospheric Plasma System for In-Line Surface Activation of Die-to-Wafer Direct and Hybrid Bonding" at Wafer Level Package Symposium 2022, and this method can also be used in the present invention.

[0146] In the method for producing a laminate of the present invention, the temperature of the plasma treatment is preferably 10° C. or higher, more preferably 30° C. or higher, and even more preferably 38° C. or higher, from the viewpoint of improving the bonding strength. On the other hand, the temperature of the plasma treatment is preferably 100° C. or lower, more preferably 60° C. or lower, and even more preferably 50° C. or lower, from the viewpoint of improving the reliability of the laminate.

[0147] In the method for producing a laminate of the present invention, from the viewpoint of improving the bonding strength and the reliability of the laminate, step (II) is preferably a step of activating the surfaces of the first substrate and the second substrate by plasma treatment in a temperature range of 30 to 100° C. The temperature of the plasma treatment is the temperature of the stage.

[0148] Generally, when the plasma treatment temperature is 30°C or higher, the effect of surface activation tends to be greater, but the arithmetic mean roughness of the treated substrate surface increases, which may result in a decrease in bonding strength. As described above, in the method for producing a laminate of the present invention, it is preferable that the resin (E) in the cured product of the resin composition (D) satisfies the condition for the content ratio of repeating units with a specific structure, or that the resin (E) contained in at least one of the (B-1) resin layer and the (B-2) resin layer satisfies the condition for the content ratio of repeating units with a specific structure. By satisfying these conditions, plasma treatment resistance is improved and an increase in arithmetic mean roughness when the plasma treatment temperature is increased can be suppressed, which is presumed to have the effect of improving bonding strength.

[0149] Furthermore, as described above, in the method for producing a laminate of the present invention, it is preferable that the cured product of the resin composition (D) satisfies the condition of an average linear expansion coefficient in a specific range, or that at least one of the (B-1) resin layer and the (B-2) resin layer satisfies the condition of an average linear expansion coefficient in a specific range. In an embodiment in which these conditions of an average linear expansion coefficient in a specific range are satisfied, when the total amount of repeating units contained in the resin (E) is taken as 100 mol%, it is preferable that the content ratio of repeating units having a rigid chemical structure, such as a phenyl group or a biphenyl group, in the resin (E) is 80 mol% or more, thereby setting the average linear expansion coefficient in the range of 0 to 40 ppm / K. Similarly, satisfying these conditions improves plasma treatment resistance and can suppress an increase in arithmetic mean roughness when the plasma treatment temperature is increased, which is presumed to have an effect of improving bonding strength.

[0150] That is, in the method for producing a laminate of the present invention, even when the temperature of the plasma treatment is set to 30° C. or higher, the effect of surface activation is improved, an increase in the arithmetic mean roughness can be suppressed, and high bonding strength can be obtained. Note that, in surface activation by plasma treatment, it is presumed that the use of a cured product or (B) resin layer having an average linear expansion coefficient of 0 to 40 ppm / K is also preferable from the viewpoint that local deformation of the substrate surface due to the heat generated can be suppressed.

[0151] For UV irradiation, known surface modification methods such as UV ozone method can be used. The substrate surface that has been subjected to plasma treatment or UV treatment is preferably brought into contact with pure water or a solvent. The pure water or solvent may be brought into contact in a liquid state or in a vapor state. It is preferable to use pure water or a solvent having a hydroxyl group. Examples of solvents having a hydroxyl group include, but are not limited to, methanol, ethanol, propanol, and isopropanol. This treatment tends to form hydroxyl groups from some of the functional groups activated by the plasma treatment, which contributes to improving bonding strength.

[0152] Furthermore, by selecting a solvent in which the resin composition (D) is soluble, the elastic modulus of the outermost surface of the cured product of the resin composition (D) is reduced and the interaction between the cured products of the resin composition (D) during bonding is improved, which tends to improve the bonding strength of the laminate. For this purpose, the substrate surface may be brought into contact with a solvent or pure water vapor before the plasma treatment.

[0153] <Step (III): Step of Bonding First Substrate and Second Substrate> The method for producing a laminate of the present invention includes the following step (III): Step (III): Bonding the first substrate and the second substrate by direct bonding, with at least a portion of the (A-1) metal electrode and the (A-2) metal electrode, and at least a portion of the (B-1) resin layer and the (B-2) resin layer or the (C) inorganic insulating layer facing each other.

[0154] Details of step (III) will be described using a specific example. In step (III), the first substrate and the second substrate are bonded by direct bonding, with at least a portion of the (A-1) metal electrode and the (A-2) metal electrode, and at least a portion of the (B-1) resin layer and the (B-2) resin layer or the (C) inorganic insulating layer facing each other.

[0155] The method for bonding the first substrate and the second substrate may be a wafer-to-wafer (W2W) process, which bonds wafers together using a wafer bonder, a chip-to-wafer (C2W) process, which bonds a chip to a wafer, or a chip-to-chip (C2C) process, which bonds chips together. Among these, the C2W process is preferred from the standpoint of bonding accuracy, freedom of circuit design, etc. Figure 1 shows a schematic cross-sectional view of a laminate produced by the W2W process, and Figure 2 shows a schematic cross-sectional view of a laminate produced by the C2W process.

[0156] A flip-chip bonder or the like is used for bonding using chips. Chips are obtained by dicing a wafer. A method for manufacturing a stack using the C2W process involves, for example, preparing multiple individual first substrates by dicing and directly bonding the multiple first substrates side-by-side on a second substrate. That is, it is preferable that multiple individual first substrates are directly bonded on the same surface of the second substrate. Alternatively, after bonding the individual first substrates to the second substrate, exposed metal electrodes and a resin layer can be formed on the surface opposite the bonding surface (or exposed metal electrodes and a resin layer can be formed on both sides of the first substrate in advance), and then bonding the resulting substrate to another first substrate in a vertically aligned manner. This allows for a high-density stacking of many chips. The multiple first substrates may be the same or different sizes.

[0157] In step (III), the temperature of the bonding stage when bonding the first substrate and the second substrate is preferably 50° C. or higher, more preferably 100° C. or higher, and even more preferably 150° C. or higher, from the viewpoints of improving the bonding strength and the reliability of the laminate. On the other hand, the temperature of the bonding stage is preferably 250° C. or lower, more preferably 230° C. or lower, and even more preferably 200° C. or lower, from the viewpoints of reducing the process time and improving the reliability of the laminate.

[0158] In step (III), the temperature of the bonding head when bonding the first substrate and the second substrate is preferably 50° C. or higher, more preferably 100° C. or higher, and even more preferably 150° C. or higher, from the viewpoints of improving the bonding strength and the reliability of the laminate. On the other hand, the temperature of the bonding head is preferably 250° C. or lower, more preferably 230° C. or lower, and even more preferably 200° C. or lower, from the viewpoints of reducing the process time and improving the reliability of the laminate.

[0159] In the method for producing a laminate of the present invention, from the viewpoints of improving the bonding strength, improving the reliability of the laminate, and reducing the process time, it is preferred that in step (III), when the first substrate and the second substrate are bonded, the temperatures of the bonding stage and the bonding head are both 250°C or less, and at least one of the temperatures of the bonding stage and the bonding head is 50°C or higher.

[0160] When the above-mentioned step (II) is a step of activating the surfaces of the first substrate and the second substrate by plasma treatment in a temperature range of 30 to 100°C, from the viewpoints of improving the bonding strength, improving the reliability of the laminate, and reducing the process time, it is preferable that the temperature of the bonding stage and the temperature of the bonding head when bonding the first substrate and the second substrate in step (III) are both 250°C or less, and at least one of the temperatures of the bonding stage and the bonding head is 50°C or more. This is because, by setting the temperature of the plasma treatment in the above range, the effect of surface activation is improved, and sufficient bonding strength can be maintained even when the bonding temperature (temperature of the bonding stage and the temperature of the bonding head) in step (III) is lowered, and it is presumed that the effect of achieving both improved bonding strength and improved reliability of the laminate is achieved.

[0161] In step (III), the bonding pressure when bonding the first substrate and the second substrate is preferably 0.1 MPa or more, more preferably 0.3 MPa or more, and even more preferably 0.5 MPa or more, from the viewpoint of improving the bonding strength. On the other hand, the bonding pressure is preferably 10.0 MPa or less, more preferably 2.0 MPa or less, and even more preferably 1.0 MPa or less, from the viewpoint of improving the reliability of the laminate by suppressing damage to the substrate body and the semiconductor element formed on the substrate.

[0162] In the method for producing a laminate of the present invention, from the viewpoint of improving the bonding strength and the reliability of the laminate, it is preferable that the bonding pressure when bonding the first substrate and the second substrate in step (III) is 0.1 to 1.0 MPa.

[0163] When the above step (II) is a step of activating the surfaces of the first substrate and the second substrate by plasma treatment in a temperature range of 30 to 100° C., from the viewpoint of improving the bonding strength and the reliability of the laminate, it is preferable that the bonding pressure when bonding the first substrate and the second substrate in step (III) is 0.1 to 1.0 MPa. This is because, by setting the temperature of the plasma treatment in the above range, the effect of surface activation is improved, and it is presumed that sufficient bonding strength can be maintained even when the bonding pressure in step (III) is reduced, thereby achieving the effects of improving both the bonding strength and the reliability of the laminate.

[0164] In the method for producing a laminate of the present invention, when the plasma treatment temperature is 30°C or higher, the contribution of hydrophilization due to surface activation increases, and sufficient bonding strength can be obtained with a lower bonding pressure. As a result, even when the bonding pressure is 1.0 MPa or lower, the bonding strength can be improved, which is preferable. Therefore, it is estimated that by setting the plasma treatment temperature to 30°C or higher, it is possible to achieve both improved bonding strength and improved reliability at a high level.

[0165] After step (III), it is preferable to perform an annealing treatment. By performing the annealing treatment, the bonding strength is improved by softening the resin layer and diffusing the metal electrodes, and the reliability of the resulting laminate is improved. The annealing temperature can be selected appropriately from a temperature range of 100°C to 350°C, and the annealing time can be selected from 3 minutes to 3 hours depending on the purpose. Among these, annealing at a temperature range of 150°C to 250°C is preferable because it puts less strain on the substrate body.

[0166] From the viewpoints of improving the bonding strength and the reliability of the laminate, the annealing temperature is preferably 50° C. or higher, more preferably 100° C. or higher, and even more preferably 150° C. or higher. On the other hand, from the viewpoint of reducing the process time, the annealing temperature is preferably 350° C. or lower, and more preferably 300° C. or lower. Furthermore, from the viewpoints of reducing the process time and improving the reliability of the laminate, the annealing temperature is preferably 250° C. or lower, more preferably 230° C. or lower, and even more preferably 200° C. or lower.

[0167] From the viewpoints of improving the bonding strength, improving the reliability of the laminate, and reducing the process time, the method for producing the laminate of the present invention preferably includes a step of performing an annealing treatment at a temperature of 150°C or higher and 250°C or lower after step (III).

[0168] <Laminate> The laminate of the present invention comprises the cured product of the present invention. The laminate of the present invention is obtained by the laminate manufacturing method described above, and has a shape in which the surfaces of the first substrate and the second substrate, which have the (A-1) metal electrode and the (A-2) metal electrode, and the (B-1) resin layer and the (B-2) resin layer, or the (B-1) resin layer and the (C) inorganic insulating layer, are bonded together. The bonded interface does not need to be clearly distinguished. Furthermore, the bonded positions of the electrodes (A-1) and (A-2) may be shifted within a range in which electrical conduction is achieved between the electrodes. For example, there may be a portion where the (A-1) metal electrode and the (B-2) resin layer, or the (A-2) metal electrode and the (B-1) resin layer, are bonded together.

[0169] The (A-1) metal electrode and the (A-2) metal electrode of the laminate are preferably made of the same metal, but may be made of different metals. The (A) metal electrode can be made of metals such as copper, gold, silver, aluminum, platinum, titanium, chromium, molybdenum, zinc, nickel, and magnesium. It may also be an alloy or laminate of these metals. It may also be a conductive metal oxide such as ITO or ZnO. Among these, copper electrodes and copper electrodes equipped with a barrier metal are preferred from the viewpoints of electrical conductivity, thermal conductivity, and economy (cost). Examples of barrier metals include nickel, chromium, and molybdenum. When the (A) metal electrode is a copper electrode, it is preferable for the thickness of the oxide film at the electrode bonding interface to be 0 nm or more and 200 nm or less, as this reduces the resistance of the electrode.

[0170] The (B-1) resin layer and the (B-2) resin layer of the laminate are formed from the cured product of the present invention, and are preferably made of the same type of resin, but may be made of different types of resin. ２Preferably, the laminate is formed from at least one of a silicon nitride film, a silicon nitride film, and a silicon carbide film. In addition, a laminate obtained from a first substrate and a second substrate using a substrate on which a circuit of a passive component and / or an active component is formed as a substrate main body has a function as a semiconductor.

[0171] The bond strength between the first substrate and the second substrate of the laminate of the present invention in a die shear test is usable if it is 5 MPa or more, but from the viewpoint of reliability, it is preferably 20 MPa or more, and more preferably 25 MPa or more.

[0172] <Semiconductor Device> The semiconductor device of the present invention is a semiconductor device including the laminate of the present invention. Examples of the semiconductor device of the present invention include a CMOS sensor and a high bandwidth memory, and the use of the laminate of the present invention in a chip bonding portion provides high reliability.

[0173] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0174] <Method for manufacturing laminate, and method for measuring physical properties of resin layer and resin composition> First, a method for manufacturing a laminate, and a method for measuring physical properties of a resin layer and a resin composition will be described. Also, schematic cross-sectional views showing a manufacturing process of a laminate using a W2W process or a C2W process are shown in FIGS. 3 and 4 .

[0175] (1) Preparation of Cu Pads and Substrates with Resin Layers (1-1) Formation of Metal Electrodes A Ti / Cu seed layer was formed on an 8-inch silicon wafer by sputtering, and a commercially available dry film resist for plating was laminated and patterned to form vias (5 x 5 rows) with a diameter of 5 μm and a pitch of 10 μm. Subsequently, Cu was formed to a height of 3 μm by electroplating. The resist was then removed with a stripping solution, and the seed layer was further removed with an etchant to form Cu pads with a diameter of 5 μm and a height of 3 μm on the 8-inch silicon wafer (see Figures 3-b and 4-b).

[0176] (1-2) Formation of Resin Layer The resin composition obtained in the example described below was spin-coated (1000 rpm, 30 seconds) onto the substrate with Cu pads prepared in (1-1) above, pre-baked (120°C for 3 minutes), cured (200°C for 1 hour, O ２ Concentration: 20 ppm by volume) was carried out to obtain a resin layer having a thickness of 4 μm (see FIGS. 3-c and 4-c).

[0177] (2) Planarization of the Substrate Using silica slurry and a urethane polishing pad, the Cu pad and the substrate with the resin layer prepared in (1-2) above were subjected to chemical mechanical polishing (CMP) (see Figures 3-d and 4-d). This process yielded a first substrate and a second substrate each having an exposed metal electrode (A) and an exposed resin layer (B) on the same surface of the substrate body.

[0178] (3) Dividing the Substrate into Individual Pieces (3-1) Fabrication of 1 mm×1 mm Chips The first substrate was divided into individual pieces (1 mm×1 mm) using a DAD3240 dicing saw (manufactured by Disco Corporation) (see FIG. 4-e).

[0179] (3-2) Fabrication of 6 mm×6 mm Chips The first substrate was diced into individual chips (6 mm×6 mm) using a DAD3240 dicing saw (manufactured by Disco Corporation) (see FIG. 4-e).

[0180] (4) Substrate Activation (4-1) Plasma Activation (Room Temperature) Using an Atmospheric Plasma System (manufactured by Ontos Equipment System), N ２ Plasma treatment of the first and second substrates was performed using a gas atmosphere of 98% by volume of H and 2% by volume of He. The total gas flow rate was 15 slpm, the power was 80 W, the distance between the plasma device and the substrate surface was 1 mm, and the speed of the plasma device was 1 mm / sec. The substrate temperature was confirmed by measuring the temperature of the stage.

[0181] (4-2) Plasma Activation (Heating) Plasma treatment of the first and second substrates was performed using an SPC-100B+H (manufactured by Hitachi High-Tech Instruments Co., Ltd.). The treatment was performed for 20 seconds with an Ar gas flow rate of 15 slpm and a power of 80 W. The substrate temperature was adjusted by adjusting the temperature setting of the stage.

[0182] (5) Fabrication of Laminate (5-1) Fabrication of W2W Laminate (High-Pressure Bonding) The surfaces of the first substrate and the second substrate (however, the first substrate was not singulated) that had been plasma-treated in (4-1) above, on which the (A) metal electrode and the (B) resin layer were exposed, were placed facing each other, and W2W bonding was performed using a vacuum press machine VACUUM STAR (manufactured by Mikado Technos Co., Ltd.), at room temperature, a pressure of 2 MPa, for 3 minutes at a vacuum degree of 50 Pa. Thereafter, annealing treatment was performed at 250°C for 1 hour in a nitrogen atmosphere (see FIG. 3-e).

[0183] (5-2) Preparation of C2W laminate (high pressure bonding) A chip (first substrate) singulated in (3-1) above and activated in (4-1) above and a wafer (second substrate) flattened in (2) above and activated in (4-1) above were prepared, and the chip was bonded to the wafer using a flip-lip bonder FC-3000S (manufactured by Toray Engineering Co., Ltd.) at 150°C, 10N, and 3 seconds. Then, an annealing treatment was performed at 250°C for 1 hour (see FIG. 4-f).

[0184] (5-3) Fabrication of W2W Laminate (Low Pressure Bonding) The surfaces of the first substrate and the second substrate (however, the first substrate was not singulated) plasma-treated in (4-2) above, on which the (A) metal electrode and the (B) resin layer were exposed, were placed facing each other, and W2W bonding was performed using a vacuum press machine VACUUM STAR (manufactured by Mikado Technos Co., Ltd.) at room temperature, a pressure of 1.0 MPa, for 3 minutes at a vacuum degree of 50 Pa. Thereafter, annealing treatment was performed at 250°C for 1 hour in a nitrogen atmosphere (see FIG. 3-e).

[0185] (5-4) Preparation of C2W laminate (low pressure bonding) A chip (first substrate) singulated in (3-2) above and activated in (4-2) above and a wafer (second substrate) planarized in (2) above and activated in (4-2) above were prepared, and the chip was bonded to the wafer using a flip-lip bonder FC-3000S (manufactured by Toray Engineering Co., Ltd.) at 150°C for 3 seconds under pressure as shown in Table 4-2. Then, an annealing treatment was performed at 250°C for 1 hour (see FIG. 4-f).

[0186] (6) Measurement of Adhesion Strength of Laminates (6-1) Measurement of Adhesion Strength of W2W Laminates Using a DAD3240 dicing saw (manufactured by Disco Corporation), only the first substrate portion of the laminate prepared in (5-1) or (5-3) above was cut to obtain five 1 mm square individual chips (the second substrate retained the shape of the original substrate). A razor blade was inserted from the edge of the laminate, and the first substrate was peeled off from the second substrate so as to leave only the individual chips. For each chip remaining on the second substrate, a lateral force was applied to the chip using a die shear measurement device (manufactured by DAGE, Series 4000), and the force at which the chip peeled off was measured. The measured value was converted to adhesive strength per unit area by dividing by the area of ​​the chip, and the average of the five values ​​was used as the adhesive strength of the W2W laminate. Furthermore, the same sample was subjected to a die shear test after undergoing a PCT treatment for 100 hours under conditions of 121°C, 2 atmospheres, and 100% RH using a pressure cooker test (PCT) device (HAST CHAMBER EHS-211MD, manufactured by Tabai Espec Corporation).

[0187] (6-2) Measurement of Adhesion Strength of C2W Laminates: For each of the five chips (first substrates) in the C2W laminates prepared in (5-2) or (5-4) above, a lateral force was applied to the chip using a die shear measurement device (DAGE, Series 4000) to measure the force at which the chip peeled off. The measured value was converted to adhesive strength per unit area by dividing it by the area of ​​the chip, and the average of the five values ​​was used as the adhesive strength of the C2W laminate. Furthermore, for the same samples, a die shear test was performed after PCT treatment for 100 hours under conditions of 121°C, 2 atmospheres, and 100% RH using a pressure cooker test (PCT) device (Tabaiespec Corporation, HAST CHAMBER EHS-211MD). The results of the die shear test were evaluated as follows: S, A, B, and C, with S being the best, A being good, B being passing, and C being poor. S: The die shear test result was 30 MPa or more. A: The die shear test result was 25 MPa or more and less than 30 MPa. B: The die shear test result was 20 MPa or more and less than 25 MPa. C: The die shear test result was less than 20 MPa.

[0188] (7) Reliability Test of Laminate (7-1) HTS (High Temperature Storage) Test The laminate prepared in (5-1) or (5-2) above was treated at 175 ° C. for 200 hours using a hot air oven. The treated laminate was cross-sectioned using an ion milling device (Hitachi High-Technologies Corporation, IM4000) and the cross section was observed using a scanning electron microscope (SEM, Hitachi High-Technologies Corporation, S-3000N) to confirm the occurrence of peeling. As an evaluation method, the degree of peeling of the metal wiring was observed, with 0% peeling being rated as 4, more than 0% but less than 25% peeling being rated as 3, 25% or more but less than 50% peeling being rated as 2, and 50% or more peeling being rated as 1, with 2 or more being evaluated as passing.

[0189] (7-2) TC (Thermal Cycle) Test 1 The laminate prepared in (5-1) or (5-2) above was subjected to 500 cycles of treatment using a thermal cycle tester (hereinafter referred to as TC device) (manufactured by Tabai Espec Co., Ltd.), with a temperature change rate of 5 ° C. / min for 15 minutes at -45 ° C. and 125 ° C. for 15 minutes. The laminate after treatment was cross-sectioned using an ion milling device and observed with a scanning electron microscope to confirm the occurrence of cracks. As an evaluation method, the degree of cracking in the resin layer was observed, with 0 cracks being rated as 4, 1 to 3 cracks being 3, 4 to 10 cracks being 2, and 11 or more cracks being 1, with 2 or more being evaluated as passing.

[0190] (7-3) TC (Thermal Cycle) Test 2 The laminate prepared in (5-1) or (5-2) above was subjected to 500 cycles of treatment using a thermal cycle tester (hereinafter referred to as TC device) (manufactured by Tabai Espec Co., Ltd.), with a temperature change rate of 10 ° C. / min for 15 minutes at -45 ° C. and 15 minutes at 150 ° C. for 15 minutes. The laminate after treatment was cross-sectioned using an ion milling device and observed with a scanning electron microscope to confirm the occurrence of cracks. As an evaluation method, the degree of cracking in the resin layer was observed, with 0 cracks being rated as 4, 1 to 3 cracks being 3, 4 to 10 cracks being 2, and 11 or more cracks being 1, with 2 or more being evaluated as passing.

[0191] (7-4) Void Test The laminate produced in (5-1) or (5-2) above was pulverized in a chamber in an atmosphere of 25°C with a He flow of 50 mL / min, and the amount of gas generated was measured. The amount of outgassing was evaluated using GC / MS (QP2010, manufactured by Shimadzu Corporation). The measurement results were ranked as 4, 3, 2, or 1, with 4 being the best, 3 being good, 2 being passing, and 1 being poor. 4: The amount of gas generated per area of ​​the substrate bonding interface was 0.1 μL / cm ２ Less than 3: The amount of gas generated per area of ​​the substrate bonding interface is 0.1 μL / cm ２ Above, 0.5μL / cm ２ Less than 2: The amount of gas generated per area of ​​the substrate bonding interface is 0.5 μL / cm ２ Above, 1.0μL / cm ２ Less than 1: The amount of gas generated per area of ​​the substrate bonding interface is 1.0 μL / cm ２ That's all.

[0192] (8) Measurement of Elastic Modulus The resin composition was applied onto a 6-inch silicon wafer by spin coating using a coating and developing apparatus Mark-7 so that the film thickness after pre-baking at 120 ° C. for 3 minutes was 5 μm, and then pre-baked. Using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised to 200 ° C. at 3.5 ° C. / min at an oxygen concentration of 20 ppm or less, and the heat treatment was performed for 1 hour. The wafer after thermal curing was cut into a size of 5 cm square, and the elastic modulus was measured in air at 25 ° C. using a nanoindenter (manufactured by Hysitron, Triboindenter TI950) using a diamond triangular pyramid indenter (Berkovich indenter) under conditions of a maximum load of 0.1 mN and an unloading rate of 90%. The obtained value was the elastic modulus of the resin layer.

[0193] (9) Measurement of mean coefficient of linear expansion (CTE) The resin composition was applied to a 6-inch silicon wafer by spin coating using a Mark-7 coating and developing apparatus so that the film thickness after pre-baking at 120 ° C for 3 minutes was 10 μm, and then pre-baked. Then, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised to 200 ° C at a rate of 3.5 ° C / min at an oxygen concentration of 20 ppm or less, and heat treatment was performed for 1 hour. When the temperature reached 50 ° C or less, the wafer was removed and immersed in 45% by mass hydrofluoric acid for 1 minute to peel the cured product from the wafer. This film was cut into strips 1.5 cm wide and 3 cm long, and measurements were performed using a thermomechanical analyzer (manufactured by SII Nanotechnology Inc., EXSTAR6000 TMA / SS6000). In the first stage, the sample was heated to 150°C at a heating rate of 5°C / min to remove absorbed water, and in the second stage, the sample was air-cooled to room temperature at a heating rate of 5°C / min. In the third stage, the measurement was performed at a heating rate of 5°C / min. The average linear expansion coefficient of the cured resin composition was determined by calculating the average linear expansion coefficient in the temperature range of 50°C to 150°C. The average linear expansion coefficient was evaluated as follows: A, B, or C, with A being good, B being passing, and C being poor. A: Average linear expansion coefficient of 17 ppm / K or more but less than 25 ppm / K; B: Average linear expansion coefficient of 0 ppm / K or more but less than 17 ppm / K, or 25 ppm / K or more but less than 40 ppm / K; and C: Average linear expansion coefficient of less than 0 ppm / K or more than 40 ppm / K.

[0194] (10-1) Degassing Test The resin composition obtained in the examples described later was spin-coated onto an 8-inch silicon wafer (1000 rpm, 30 seconds), pre-baked (120°C for 3 minutes), cured (200°C for 1 hour, O ２ A resin layer having a thickness of 4 μm was obtained on a silicon substrate.

[0195] Using a DAD3240 dicing saw (manufactured by Disco Corporation), the silicon substrate with the 4 μm-thick resin layer was singulated into 10 mm x 20 mm strips. The amount of outgassing was evaluated by measuring the total amount of organic gases generated from 20 substrates singulated into strips by heating using the TPD-MS (Temperature Programmed Desorption-Mass Spectrometry) method. The heating conditions were a temperature increase from 25°C to 250°C at a rate of 3°C / min and a hold at 250°C for 1 hour. Helium was used as the carrier gas at a flow rate of 50 ml / min. A GC / MS (Shimadzu Corporation, QP2010) was used as the measurement device. The measurement results were graded as S, A, B, or C, with S being the best, A being good, B being passing, and C being poor. S: The amount of organic gas generated per substrate area is 10 ng / mm ２ A: The amount of organic gas generated per substrate area is less than 10 ng / mm ２ Above, 20ng / mm ２ B: The amount of organic gas generated per substrate area is less than 20 ng / mm ２ Above, 50ng / mm ２ C: The amount of organic gas generated per substrate area is less than 50 ng / mm ２ That's all.

[0196] (10-2) Degassing Test 2 The resin composition obtained in the example described later was spin-coated onto an 8-inch silicon wafer (1000 rpm, 30 seconds), pre-baked (120°C for 3 minutes), cured (200°C for 1 hour, O ２ A resin layer having a thickness of 4 μm was obtained on a silicon substrate.

[0197] Using a DAD3240 dicing saw (manufactured by Disco Corporation), the silicon substrate having the 4 μm thick resin layer was singulated into 10 mm x 20 mm strips. The amount of outgassing was evaluated by measuring the total amount of organic gas from the curing accelerator contained in the resin composition generated from 20 substrates singulated into strips by heating using the TPD-MS (Temperature Programmed Desorption-Mass Spectrometry) method. The heating conditions were a temperature increase from 25 ° C to 250 ° C at a rate of 3 ° C / min and a hold at 250 ° C for 1 hour. Helium was used as the carrier gas at a flow rate of 50 ml / min. The measurement device used was a GC / MS (Shimadzu Corporation, QP2010). The measurement results were graded as S, A, B, or C, with S being the best, A being good, B being passing, and C being poor. S: The amount of organic gas generated per substrate area was 5 ng / mm ２ A: The amount of organic gas generated per substrate area is less than 5 ng / mm ２ Above, 20ng / mm ２ B: The amount of organic gas generated per substrate area is less than 20 ng / mm ２ Above, 30ng / mm ２ C: The amount of organic gas generated per substrate area is less than 30 ng / mm ２ The above -: The resin composition does not contain a curing accelerator.

[0198] (11) Evaluation of Cyclization Rate The resin composition was applied to a 6-inch silicon wafer by spin coating using a Mark-7 coating and developing apparatus so that the film thickness after pre-baking at 120°C for 3 minutes would be 10 μm, and then pre-baked. Then, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised to 200°C at a rate of 3.5°C / min at an oxygen concentration of 20 ppm or less, and heat treatment was carried out for 1 hour. When the temperature reached 50°C or less, the wafer was removed, and the cyclization rate of the resulting cured product was measured. The cyclization rate was measured by measuring an infrared absorption spectrum and detecting the peak (1780 cm) derived from the imide structure. －１ The closest wavenumber peak is 1377 cm －１The imide ring closure rate was calculated from the intensity of the peak derived from the imide structure of the sample heat-treated at 350°C for 1 hour (the peak with the wavenumber closest to the vicinity of the sample). The intensity of the peak derived from the imide structure of the sample heat-treated at 350°C for 1 hour was defined as the peak intensity for a cyclization rate (imide ring closure rate) of 100%, and the cyclization rate (imide ring closure rate) was calculated from the intensity of the peak derived from the imide structure of the sample to be measured. The measurement results were judged as A, B, or C, with A being the best, B being good, B- being passing, and C being poor. A: cyclization rate greater than 90% B: cyclization rate greater than 80% but not more than 90% B-: cyclization rate greater than 70% but not more than 80% C: cyclization rate not more than 70%

[0199] <Resin Composition Used to Form Resin Layer (B)> Next, the resin composition used to form the resin layer (B) will be described. Abbreviations of compounds used in the synthesis examples and examples are listed below. SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane PDA: p-phenylenediamine m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl 4,4'-ODA: 4,4'-diaminodiphenyl ether 3,3'-ODA: 3,3'-diaminodiphenyl ether 3,5-DATA: 1H-1,2,4-triazole-3,5-diamine 1,3,3'-APB: 1,3'-bis-(3-aminophenoxy)benzene PMDA: pyromellitic dianhydride BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride ODPA: 4,4'-oxydiphthalic anhydride a-BPDA: 2,3,3',4'-biphenyltetracarboxylic dianhydride NMP: N-methyl-2-pyrrolidone MPA: methoxy-N,N-dimethylpropionamide DMPA: N,N-dimethylpropionamide 2E4MZ: 2-ethyl-4-methylimidazole KBM-403: 3-glycidoxypropyltrimethoxysilane (silane coupling agent) (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) IRGANOX (registered trademark) 245: ethylene bis(oxyethylene) bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate) (antioxidant) (trade name, manufactured by BASF Corporation) DAPA: N,N-dimethyl-3-(dimethylamino)propanamide.

[0200] [Synthesis Example 1] Resin (P-1) Under a dry nitrogen stream, 19.2 g (0.096 mol) of 4,4'-ODA and 0.99 g (0.004 mol) of SiDA were dissolved in 200 g of NMP. To this solution, 16.8 g (0.077 mol) of PMDA and 5.9 g (0.020 mol) of BPDA were added, and the mixture was stirred at 60°C for 5 hours to obtain a resin solution (P-1). After stirring, NMP was added so that the solids concentration became 16% by mass.

[0201] [Synthesis Examples 2 to 9, 11 to 15] Resins (P-2 to P-9, P-11 to P-15) Resins P-2 to P-9 and P-11 to P-15 were obtained in the same manner as in Synthesis Example 1, except that the raw materials and solvent were changed to achieve the ratios shown in Tables 1-1 and 1-2.

[0202] Synthesis Example 10 Resin (P-10) Under a dry nitrogen stream, 19.2 g (0.096 mol) of 4,4'-ODA and 0.99 g (0.004 mol) of SiDA were dissolved in 200 g of NMP. To this solution, 16.8 g (0.077 mol) of PMDA and 5.9 g (0.020 mol) of a-BPDA were added, and the mixture was stirred at 80°C for 8 hours to obtain a resin solution (P-10). After stirring, NMP was added so that the solids concentration became 16% by mass.

[0203] Comparative Synthesis Examples 1 to 5 Resins (HP-1 to HP-5) Resins HP-1 to HP-5 were obtained in the same manner as in Synthesis Example 1, except that the raw materials and solvent were changed to give the ratios shown in Table 1-2.

[0204] The compositions of the resins (E) obtained in Synthesis Examples 1 to 15 and Comparative Synthesis Examples 1 to 5 are shown in Tables 1-1 and 1-2. The copolymerization ratios of the monomers are as shown in Tables 1-1 and 1-2.

[0205]

[0206]

[0207] [Examples 1 to 25 and Comparative Examples 1 to 5] The resins obtained in the synthesis examples or ready-made resins were mixed with solvents and additives to obtain the mass ratios and solid content concentrations shown in Tables 2-1 and 2-2, respectively, to obtain respective resin compositions. All of the obtained resin compositions were filtered through a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) before evaluation.

[0208]

[0209]

[0210] [Examples 27 to 54 and 57 to 85; Comparative Examples 6 to 9, 11 to 16, and 18 to 19] Using the resin compositions prepared in Examples 1 to 25 and Comparative Examples 1 to 5 and commercially available resin compositions, laminates were prepared by the laminate preparation methods (1) to (5) described above, and the laminates were evaluated by the physical property measurement methods (6) to (8) for the resin layer and the resin composition. The results of each example and comparative example are shown in Tables 2-1, 2-2, 3-1, and 3-2.

[0211] [Examples 26 and 56; Comparative Examples 10 and 17] Instead of forming the resin layer in the above (1-2), SiO was formed by chemical vapor deposition using tetraethoxysilane. ２ Except for forming a coating, laminates were prepared in the same manner as in the laminate preparation methods (1) to (5) described above, and the laminates were evaluated using the physical property measurement methods (5) to (8) for the resin layer and the resin composition. The results of each example and comparative example are shown in Tables 3-1, 3-2, 4-1, and 4-2.

[0212]

[0213]

[0214]

[0215]

[0216] [Examples 1 to 25 and Comparative Examples 1 to 5] The properties of resin compositions were evaluated by the methods for measuring physical properties (9), (10), and (11). Table 5 shows the properties of each example and comparative example.

[0217]

[0218] REFERENCE SIGNS LIST 1 Substrate body (silicon wafer, etc.) 2 (A-1) Metal electrode (Cu, etc.) 3 (B-1) Resin layer 4 (B-2) Resin layer or (C) Inorganic insulating layer 5 (A-2) Metal electrode (Cu, etc.) 6 Substrate body (silicon wafer, etc.) 7 First substrate 8 Second substrate

Claims

1. A method for producing a laminate comprising steps (I), (II), and (III) in this order, wherein at least one of the (B-1) resin layer and the (B-2) resin layer is made of a cured product of a resin composition (D), and the resin composition (D) contains a resin (E) and a solvent, and the resin (E) has either or both of a repeating unit represented by formula (1-A) and a repeating unit represented by formula (1-B), and the resin (E) has either or both of a repeating unit represented by formula (1-C) and a repeating unit represented by formula (1-D), and when all repeating units contained in the resin (E) are taken as 100 mol %, the total of the repeating units represented by formula (1-A) and the repeating units represented by formula (1-B) in the resin (E) is 80 to 99 mol %, and the total of the repeating units represented by formula (1-C) and the repeating units represented by formula (1-D) in the resin (E) is 1 to 10 mol %. Step (I): Preparing a first substrate having an (A-1) metal electrode and an exposed (B-1) resin layer exposed on the same surface of the substrate body, and a second substrate having an (A-2) metal electrode and an exposed (B-2) resin layer or (C) inorganic insulating layer exposed on the same surface of the substrate body; Step (II): Activating the surfaces of the first substrate and the second substrate by plasma treatment or UV irradiation; Step (III): Bonding the first substrate and the second substrate by direct bonding, with at least a portion of the (A-1) metal electrode and the (A-2) metal electrode and at least a portion of the (B-1) resin layer facing the (B-2) resin layer or the (C) inorganic insulating layer. (In formula (1-A), formula (1-B), formula (1-C) and formula (1-D), R １ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by formula (2). Each s independently represents an integer of 1 to 50. ８ and R ９ R each independently represents an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ４ ~R ７ each independently represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group; each X independently represents a group represented by formula (3); and each Y independently represents a group represented by formula (4). (In formula (2), R １０ is an alkyl group having 1 to 5 carbon atoms, R １１ represents an alkylidene group having 1 to 5 carbon atoms. * represents a bonding site. In formula (3), n is an integer of 0 to 3, and m is an integer of 1 to 2. * represents a bonding site. In formula (4), R ２ and R ３ each independently represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a carboxy group, a sulfonic acid group, or a mercapto group. p is an integer from 0 to 4, q is an integer from 0 to 4, and r is an integer from 0 to 2. Z is a bond, atom, or group selected from a single bond, an alkylene group having 1 to 12 carbon atoms, a halogenated alkylene group having 1 to 12 carbon atoms, a sulfonyl group, an S atom, an O atom, a CO group, and a COO group. * represents a bonding site.

2. The method for producing a laminate according to claim 1, wherein the resin composition (D) contains 0.1 to 3 parts by mass of the compound represented by formula (5) per 100 parts by mass of the resin (E). (In formula (5), R １２ , R １３ , R １４ and R １５ each independently represents a group having 1 to 5 carbon atoms, 0 to 2 oxygen atoms, and 0 to 1 nitrogen atom, or a hydrogen atom.

3. The method for producing a laminate according to claim 1, wherein step (II) is a step of activating the surfaces of the first substrate and the second substrate by plasma treatment in a temperature range of 30 to 100°C.

4. A method for producing a laminate, comprising steps (I), (II), and (III) in this order, wherein at least one of the (B-1) resin layer and the (B-2) resin layer has an average linear expansion coefficient of 0 to 40 ppm / K in a temperature range of 50 to 150°C, and step (II) is a step of activating the surfaces of the first substrate and the second substrate by plasma treatment in a temperature range of 30 to 100°C. Step (I): Preparing a first substrate having an (A-1) metal electrode and an exposed (B-1) resin layer exposed on the same surface of the substrate body, and a second substrate having an (A-2) metal electrode and an exposed (B-2) resin layer or (C) inorganic insulating layer exposed on the same surface of the substrate body; Step (II): Activating the surfaces of the first substrate and the second substrate by plasma treatment or UV irradiation; Step (III): Bonding the first substrate and the second substrate by direct bonding, with at least a portion of the (A-1) metal electrode and the (A-2) metal electrode and at least a portion of the (B-1) resin layer facing the (B-2) resin layer or the (C) inorganic insulating layer.

5. A method for producing a laminate according to claim 4, wherein at least one of the (B-1) resin layer and the (B-2) resin layer comprises a cured product of a resin composition (D), the resin composition (D) contains a resin (E) and a solvent, the resin (E) has either or both of a repeating unit represented by formula (1-A) and a repeating unit represented by formula (1-B), and the resin (E) further has either or both of a repeating unit represented by formula (1-C) and a repeating unit represented by formula (1-D), and when all repeating units contained in the resin (E) are taken as 100 mol %, the total of the repeating units represented by formula (1-A) and the repeating units represented by formula (1-B) in the resin (E) is 80 to 99 mol %, and the total of the repeating units represented by formula (1-C) and the repeating units represented by formula (1-D) in the resin (E) is 1 to 10 mol %. (In formula (1-A), formula (1-B), formula (1-C) and formula (1-D), R １ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by formula (2). Each s independently represents an integer of 1 to 50. ８ and R ９ R each independently represents an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ４ ~R ７ each independently represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group; each X independently represents a group represented by formula (3); and each Y independently represents a group represented by formula (4). (In formula (2), R １０ is an alkyl group having 1 to 5 carbon atoms, R １１ represents an alkylidene group having 1 to 5 carbon atoms. * represents a bonding site. In formula (3), n is an integer of 0 to 3, and m is an integer of 1 to 2. * represents a bonding site. In formula (4), R ２ and R ３ each independently represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a carboxy group, a sulfonic acid group, or a mercapto group. p is an integer of 0 to 4, q is an integer of 0 to 4, and r is an integer of 0 to 2. Z is a bond, atom, or group selected from a single bond, an alkylene group having 1 to 12 carbon atoms, a halogenated alkylene group having 1 to 12 carbon atoms, a sulfonyl group, an S atom, an O atom, a CO group, and a COO group. * represents a bonding site.

6. The method for producing a laminate according to any one of claims 3 to 5, wherein in step (III), the first substrate and the second substrate are bonded together under a bonding pressure of 0.1 to 1.0 MPa.

7. The method for producing a laminate according to claim 3, wherein the cured product of said resin composition (D) has an average linear expansion coefficient of 0 to 40 ppm / K in the temperature range of 50 to 150°C.

8. The method for producing a laminate according to any one of claims 1 to 5, wherein step (I) includes a smoothing step using at least one of chemical mechanical polishing and surface planing.

9. A method for manufacturing a laminate according to any one of claims 1 to 5, wherein in step (III), when bonding the first substrate and the second substrate, the temperature of the bonding stage and the temperature of the bonding head are both 250°C or less, and at least one of the temperature of the bonding stage and the temperature of the bonding head is 50°C or higher.

10. The method for producing a laminate according to any one of claims 1 to 5, further comprising a step of performing an annealing treatment at a temperature of 150°C or higher and 250°C or lower after the step (III).

11. A resin composition comprising a resin (E) and a solvent, wherein the resin (E) has either or both of repeating units represented by formula (1-A) and repeating units represented by formula (1-B), and the resin (E) further has either or both of repeating units represented by formula (1-C) and repeating units represented by formula (1-D), and when all repeating units contained in the resin (E) are taken as 100 mol %, the total of the repeating units represented by formula (1-A) and the repeating units represented by formula (1-B) in the resin (E) is 80 to 99 mol %, and the total of the repeating units represented by formula (1-C) and the repeating units represented by formula (1-D) in the resin (E) is 1 to 10 mol %. (In formula (1-A), formula (1-B), formula (1-C) and formula (1-D), R １ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by formula (2). Each s independently represents an integer of 1 to 50. ８ and R ９ R each independently represents an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms. ４ ~R ７ each independently represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group; each X independently represents a group represented by formula (3); and each Y independently represents a group represented by formula (4). (In formula (2), R １０ is an alkyl group having 1 to 5 carbon atoms, R １１ represents an alkylidene group having 1 to 5 carbon atoms. * represents a bonding site. In formula (3), n is an integer of 0 to 3, and m is an integer of 1 to 2. * represents a bonding site. In formula (4), R ２ and R ３ each independently represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a carboxy group, a sulfonic acid group, or a mercapto group. p is an integer of 0 to 4, q is an integer of 0 to 4, and r is an integer of 0 to 2. Z is a bond, atom, or group selected from a single bond, an alkylene group having 1 to 12 carbon atoms, a halogenated alkylene group having 1 to 12 carbon atoms, a sulfonyl group, an S atom, an O atom, a CO group, and a COO group. * represents a bonding site.

12. The resin composition according to claim 11, which contains 0.1 to 3 parts by mass of the compound represented by formula (5) per 100 parts by mass of the resin (E). (In formula (5), R １２ , R １３ , R １４ and R １５ each independently represents a group having 1 to 5 carbon atoms, 0 to 2 oxygen atoms, and 0 to 1 nitrogen atom, or a hydrogen atom.

13. The resin composition according to claim 11 or 12, which contains 0.001 to 3 parts by mass of N,N-dimethyl-3-(dimethylamino)propanamide per 100 parts by mass of the resin (E).

14. A cured product obtained by curing the resin composition according to claim 11 or 12.

15. A laminate comprising the cured product according to claim 14.

16. A semiconductor device comprising the stack of claim 15.

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